Apparatus for powerful energy transfer technique

ABSTRACT

In addition to the apparatus disclosed in the prior patent applications of which this application is a continuation-in-part, a reaction chamber is provided with mercury vapor quartz discharge lamps. In close proximity to the lamps are spheres, or thin continuous wires, or filaments or other physical configurations of laser-type material which produce relatively coherentradiation in a manner similar to lasers. The spheres or filaments include concentric partially reflective surfaces, and include an active material which is pumped by the efficient spectral radiation of the mercury vapor, and radiates at a frequency or frequencies matched to the absorption characteristics of the feedstock being fed through the reaction chamber. The laser-type material may be operated to produce output radiation at a harmonic, such as the second, third, fourth or higher harmonic of the basic laser radiation, and these harmonic output radiations may be enhanced by using semi-reflective coatings which reflect in the order of 70% to 90% of the radiation, particularly in the case of spheres. High energy content ultraviolet radiation may also be generated by the &#34;beating&#34; of radiant energy from the mercury vapor tubes and the laser-type material. Efficiency is enhanced by chain reactions which occur with the feedstock materials being fed to the reaction chamber, and these chain reactions involve the generation and regeneration of excited atoms of oxygen or other substances.

REFERENCE TO RELATED PATENT APPLICATIONS

This application is a continuation-in-part of my two prior co-pendingPat. applications:

U.S. Pat. Application Ser. No. 790,320, filed Apr. 25, 1977, entitled"High Intensity Energy Transfer Technique", and these chain reactionsinvolve the generation and regeneration of excited atoms of oxygen orother substances; and

U.S. patent Application Ser. No. 834,682, filed Sept. 19, 1977, entitled"High Efficiency Energy Transfer Technique", now U.S. Pat. No.4,113,589, granted Sep. 12, 1978.

FIELD OF THE INVENTION

This invention related to highly efficient photochemical techniques.

BACKGROUND OF THE INVENTION

It has been proposed heretofore to apply coherent radiation fromconventional lasers to gases to dissociate them. However, suchapplication of laser energy is highly inefficient, and is noteconomically practical for commercial processes.

Accordingly, a principal object of the present invention is topractically and economically apply intense relatively coherent radiationto chemical substances to dissociate them, and initiate additionalreactions.

SUMMARY OF THE INVENTION

In accordance with one aspect of the invention, a reaction chamber isprovided with a number of gas discharge tubes, and closely associatedmaterial capable of being pumped to excited states and emittingrelatively coherent radiation of high intensity. Feedstock is suppliedto the reaction chamber and is exposed to the radiation, which floodsthe reaction chamber. Further, the feedstock has absorption bands atcertain frequencies, and the gas discharge and the associated laser-typematerial are chosen to provide intense output radiation at one or moreof the absorption bands of the feedstock.

Additional gases may be supplied to the reaction chamber to react withthe products formed when the basic feedstock is dissociated.

In accordance with one particular aspect of the invention the laser-typematerial may be in the form of filaments, wires or spheres, and may alsobe provided with one or more semi-transparent concentric reflectingsurfaces accurately spaced to reinforce the coherent output radiation.

One particularly advantageous form of the invention involves the use ofa large number of spheres of laser-type material secured to the outersurface of the gas discharge tubes. The spheres are provided with asemi-reflecting outer metallic coating, but this is not present on thatportion of the spheres adjacent the gas discharge tubes to permit easyentry of the pumping radiation from the gas discharge tube. When it isdesired to provide increased high frequency output radiation, by thegeneration of harmonics of the basic output radiation frequency of thelaser type material, the reflective coating should be in the order of70% to 90% reflecting.

In accordance with a subordinate feature of the invention, instead ofnormal reflecting materials such as chromium or nickel, for example,metallic coatings may be employed which are reflective to visible andinfrared frequencies but are relatively transparent to shorterwavelength ultraviolet radiation.

The use of mercury vapor gas in discharge tubes having quartz envelopesis preferred, in view of the many spectral lines of mercury vapor whichare useful for pumping the laser-type material. Ruby laser material,aluminum oxide doped with chromium, may suitably be employed as thelaser-type material; but other laser-type materials having differentoutput radiation frequencies should be used as required to match theabsorption bands of the feedstocks supplied to the reaction chamber.

Another feature of the invention involves the beating together ofradiation at different frequencies in the presence of mediadiscontinuities in the form of the feedstock to be irradiated, and theresultant generation of sum and difference frequencies appropriate tocouple strongly with absorption bands of the feedstock material. Thistechnique is particularly advantageous when the feedstock has absorptionbands in the ultraviolet frequency spectrum.

In accordance with another specific aspect of the invention, thefeedstock may be water vapor and air may also be supplied to thereaction chamber. When high intensity radiation within the ultravioletor other absorption band of water vapor is radiated throughout thereaction chamber, the water vapor is split into hydrogen and activatedoxygen atoms. These activated oxygen atoms combine with additional watervapor to form hydrogen and/or hydrogen peroxide, in additional reactionsforming part of a chain reaction initiated by the basic irradiation.

In accordance with another important feature of the invention, at leasttwo feedstocks are supplied to a reaction chamber, and the reactionchamber is flooded with radiation within at least one of the absorptionbands of one of said feedstocks at an intensity level sufficient todissociate the feedstock and the dissociation products are maintained insaid reaction chamber at concentrations sufficient to create a chainreaction with the incoming feedstocks.

Another feature of the invention involves applying radiation ofdifferent frequencies to the input section as compared with the outputsection of the reaction chamber, to facilitate relatively completeirradiation and dissociation of the incoming feedstock and avoidingdissociation of the desired product gases. For example, in the case ofwater vapor as one of the feedstocks and hydrogen peroxide as one of theproduct gases, both water vapor and hydrogen peroxide have highabsorption bands in the ultraviolet frequency spectrum; and water vapor,but not hydrogen peroxide, has absorption bands in the infraredfrequency range. Accordingly, the more powerful U-V radiations may beemployed in the input section of the reaction chamber, to dissociatewater vapor; but in the output section where a substantial proportion ofhydrogen peroxide will be present, infrared radiation may be employed toselectively dissociate the water vapor without dissociating the hydrogenperoxide. Similar considerations are of course applicable to otherfeedstock and product gases, taking into consideration their absorptioncharacteristics, and relative responsiveness to radiation of differentfrequencies.

A feature of the invention involves the introduction of additional airinto the reaction chambers to combine with the hydrogen which isdissociated from water vapor to produce hydrogen peroxide, with thecollateral advantage of supplying heat to the reaction chamber from thisexothermic reaction.

Other objects, features, and advantages of the invention will becomeapparent from a consideration of the following detailed description, andfrom the accompanying drawings.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 is a schematic representation of one illustrative embodiment ofthe system of the present invention;

FIG. 2 is a perspective view of the hydrogen burner/heating means whichmay be employed as part of the system;

FIG. 3 is a vertical cross-section of the hydrogen burner of FIG. 2;

FIG. 4 is a perspective view partially broken away for illustrativeclarity of a reaction chamber;

FIG. 5 is a perspective view, also partially broken away, of a completesystem;

FIG. 6 is a block diagram of a system illustrating certain principles ofthe present invention;

FIG. 7 is a pressure versus time plot for a multiple reaction chambersystem;

FIG. 8 is a cross-sectional view of a portion of a reaction chamberassembly which may be employed;

FIG.9 is a schematic diagram of the structural relationship of aplurality of reaction chambers, central burner, and enclosing insulatinghousing for use in a system of the present invention;

FIG. 10 is a plot of the absorption characteristics of water vaporversus wave length;

FIG. 11 is a showing of the contents of each of the reaction chambersemployed in the one embodiment of the invention;

FIG. 12 is a schematic diagram indicating the generation of concentratedradiation and its application to a feedstock;

FIG. 13 shows an alternative apparatus involving the continuous flow offeedstock.

FIG. 14 is a plot of Photon Emission from a "Black Body" at 1000° K.versus Wavelength;

FIG. 15 is a plot of Radiant Emittance vs. Wavelength for a 1000° K.black body;

FIG. 16 shows a wire coated with radiation-producing material;

FIGS. 17 and 19 show reaction chambers for applying high frequencyradiant energy to feedstocks;

FIG. 18 is a diagram showing the reaction chambers of FIGS. 17 and 19includes in an operative system;

FIG. 20 is a detailed showing of one arrangement for supporting theradiating wires of FIGS. 16, 17 and 19;

FIG. 21 shows the ultraviolet absorption characteristic of hydrogenperoxide, H₂ O₂ ;

FIGS. 22 and 23 are side and sectional views, respectively, of areaction chamber which is irradiated by light from two lasers ofdifferent frequencies;

FIG. 24 is a schematic view of reaction chamber containing gas dischargetubes, in accordance with the invention;

FIG. 25 is an enlarged cross-sectional view of one end of the reactionchamber of FIG. 24;

FIG. 26 is an enlarged schematic view of one of the plates which dividesthe reaction chamber of FIG. 24;

FIG. 27 is a cross-sectional view through one of the filaments includinglaser-type material which may be wrapped on the discharge tube of FIG.24;

FIG. 28 is a schematic showing of another type of filament which may bewrapped on the gas discharge tubes of FIG. 24;

FIG. 29 includes a pair of graphs of the absorption coefficient of watervapor in the ultraviolet frequency range;

FIG. 30 is a showing of a plurality of spheres of laser-type materialwhich may be mounted on the outer surface of the gas discharge tubesshown in FIGS. 24 and 25 of the drawings;

FIG. 31 is a schematic showing of pumping radiationapplied to alaser-type material sphere mounted on the exterior surface of one of thegas discharge tubes, and the corresponding coherent output radiationfrom the sphere; and

FIG. 32 is a schematic showing of the generation of pumping radiationfrom the gas discharge tubes and its application to the laser-typespheres that are in close proximity to the feedstock and product gasesin the reaction chamber.

Initially, before considering the drawings in detail, it may be notedthat FIG. 1 through 23 were included in the prior co-pending patentapplications, Ser. Nos. 790,320, and 834,682, of which thisspecification is a Continuation-in-Part. FIGS. 24 through 32 are newlyadded in the present specification and represent the preferredembodiments of the invention. The following description of FIGS. 1through 23 will closely parallel that set forth in the prior patentapplication, Ser. No. 834,682 cited hereinabove.

DETAILED DESCRIPTION

Turning now to FIG. 1, the system of the present invention is generallydesignated by the numeral 10 and it comprises reaction chambers 12, 14,16 and 18, heating means generally designated 20, and a hydrogen andhydrogen peroxide reservoir or accumulator 22. Water enters the systemat conduit 24, passes through flow control valve 26 and conduit 28 tomanifold 30. Water may then be supplied to heat exchange coil 32 throughvalve 34 and conduit 36, to heat exchange coil 38 through valve 40 andconduit 42, to heat exchange coil 44 through valve 46 and conduit 48,and to heat exchange coil 50 through valve 52 and conduit 54. It will beseen that conduit 36 is the inlet end of heat exchange coil 32, theoutlet of heat exchange coil 32 being conduit 56 which is connected toone end of reaction chamber 12. Similarly, the outlet end of heatexchange coil 38 is conduit 58 connected to one end of reaction chamber14, the outlet end of heat exchange coil 44 is connected to one end ofreaction chamber 16 through conduit 60, and the outlet end of heatexchange coil 50 is connected to one end of reaction chamber 18 throughconduit 62.

Vacuum is applied to the system, for purposes which will become apparentas the description proceeds, through conduit 64, flow control valve 66,and conduit 68 which is connected to one end of a conventional gasburner 70. It will be appreciated that heating means 20 comprises burner70 and heat exchange coils 32, 38, 44, and 50, and their respectiveconduits and valves.

As will also become apparent as the description proceeds, hydrogen andhydrogen peroxide generated in the reaction chambers 12, 14, 16, and 18passes through conduits 72, 74, 76 and 78, respectively and valves 80,82, 84 and 86, respectively, to manifold 88. The hydrogen and/orhydrogen peroxide then passes through conduit 90 with check valve 92 tohydrogen accumulator 22 where it is then drawn off for use throughconduit 94, flow control valve 96, and conduit 98. Conduit 100, flowcontrol valve 102 and conduit 104 are provided to allow atmospheric airto enter the system when and if needed, as will be described more fullyhereinbelow.

Before proceeding further with a description of the system, it should bedistinctly understood that while the example given herein for purelyillustrative purposes includes four reaction chambers, there is, infact, no limit other than practical considerations of size and weight asto the number of reaction chambers used. In fact, the invention could bepracticed with as few as one reaction chamber and as many reactionchambers as desired, there being no reason why a bank of dozens or evena hundred reaction chambers could not be used. For this reason,applicant is not limiting himself to the use of four reaction chambersexcept for illustrative purposes. Obviously, one skilled in the artwould easily be able to include the necessary valve elements and otherhardware if he were adding more reaction chambers.

With the foregoing understood, the description of the instant inventivesystem will proceed. The system runs at about 900° K. or 1000° K. andmay be pre-heated by any well-known electrical heating means such asthat described in the parent application.

Alternatively, pre-heating can be accomplished by burning hydrogen inburner 70, the hydrogen being the "tailings" left in one or more of thereaction chambers from a previous run of the system. For thispre-heating cycle, flow control valve 26 is opened to allow water toenter the system filling manifold 30. Valves 34, 40, 46 and 52 remainclosed during this cycle. Valves 106, 108, 110 and 112 are opened.Vacuum is applied at conduit 64 with valve 66 opened. Thus, it will beseen that vacuum is applied via conduit 68 to burner 70. Since the otherend of burner 70 is connected to conduit 114 which, in turn, isconnected to manifold 116, manifold 116 is under vacuum. Then, sincevalves 106, 108, 110, and 112 are open, the vacuum is applied toreaction chambers 12, 14, 16 and 18, respectively, through conduits 118,120, 122 and 124, respectively. Thus, any residual hydrogen tailingsremaining in any of the reaction chambers is drawn into the inlet end ofburner 70 to be burned along with any residual oxygen tailings or withatmospheric air drawn in through conduit 100 and valve 102 by the vacuumwhich also affects this air line. It should also be noted that in eventof a "cold" start where there are no hydrogen tailings to be burned, acombustible gas, such as hydrogen, could be drawn in through conduit 100and valve 102 to provide the initial start-up heat. The burning ofhydrogen in burner 70 provides considerable heat which, by radiation andconduction is passed to the reaction chambers which are filled withreactant 126. When the system is pre-heated to a sufficiently hightemperature, we are ready to proceed with the generation of hydrogen andhydrogen peroxide.

Valve 34 is opened to allow a predetermined amount of water to enterheat exchange coil 32 which is, in essence, a steam generator. The wateris "flashed" to steam and delivered through conduit 56 to the inlet endof reaction chamber 12. The steam enters reaction chamber 12 containingreactant 126 to fill the total void volume and is constrained in thisvolume because all outlet valves are closed. The residence time, orreaction time, may be controlled from a few seconds (typically about 2to about 3 seconds) to a rather long time (typically about 60 seconds),depending on the reactant used, the particulate size, the temperature,and the pressure. Valves 108, 110, and 112 are fully opened to allow thevacuum evacuation of all residual gases in the other reaction chambersand their respective heat exchangers and piping. It should be noted thatsince a predetermined amount of water was to be passed to heat exchangecoil 32, valve 34 was opened for just a brief period and then closed.

Steam having entered and permeated reactant 126 in reaction chamber 12,valve 40 is then opened briefly to allow a metered amount of water intoheat exchange coil 38, with the steam generated therein then passingthrough conduit 58 to reaction chamber 14. Valve 40 is then closed. Thesteam which passes into reaction chamber 14, as with the steam wich hadpassed into reaction chamber 12, is converted into hydrogen and/orhydrogen peroxide and then held restrained in the reaction chamber forthe predetermined control time. In the meantime, valve 80 is opened sothat the pressure built up in reaction chamber 12 will force thehydrogen to exit through conduit 72 and valve 80 into manifold 88 andthen through check valve 92 into the hydrogen accumulator 22. Valve 80is then closed and valve 106 is opened to allow the vacuum to empty theresidual hydrogen and oxygen tailings from reaction chamber 12 and passit to burner 70 where the mixture is burned using disproportionatedoxygen from reaction chambers 12, 16, and 18 along with additionalatmospheric oxygen supplied through conduit 100, if necessary. It shouldbe noted that when valve 80 was opened to pass the hydrogen and/orhydrogen peroxide out of chamber 12, and then vacuum was applied byopening valve 106, the oxidized reactant in chamber 12 disproportionatedto release the bound oxygen since the temperature in the reactionchamber remained high and the presure was lowered.

With valve 106 still open, valve 82 is also opened to allow the hydrogenand/or hydrogen peroxide generated in reaction chamber 14 to flow intothe manifold 88 from which it is directed into the hydrogen reservoir22. In the meantime, valve 46 had briefly opened to allow a meteredamount of water into heat exchange coil 44 and then the steam formed inheat exchange coil 44 passes to the inlet end of reaction chamber 16. Atthis point, valve 84 is still closed. Valves 106 and 112 are still opento allow vacuum to exhaust chambers 12 and 18.

Valve 82 then closes and valve 108 opens along with valves 106 and 112which are also open. Thus, hydrogen and/or hydrogen peroxide and oxygentailings are being conveyed through valve 108 to burner 70 forcombustion with the combustion gases being exhausted through conduit 68.

Then, valve 84 is opened to pass the hydrogen and/or hydrogen peroxidefrom reaction chamber 16 to manifold 88. Valves 106 and 108 are openedto allow vacuum to exhaust the respective chambers 12 and 14 while valve52 has been allowed to briefly open to pass a metered amount of water toheat exchange coil 50 with the steam being formed then passing toreaction chamber 18. The steam in reaction chamber 18 reacts withreactant 126 to form hydrogen and/or hydrogen peroxide which isrestrained since valve 86 is still closed. Valves 106, 108 and 110 areall open so that the other reaction chambers are being exhausted.

Valve 88 is then opened to relieve the pressure on reaction chamber 18and allow the hydrogen and/or hydrogen peroxide to pass to manifold 88.At this point, the whole cycle starts again and valve 14 is brieflyopened to allow a metered amount of water to pass to heat exchange coil32, valve 86 is closed, and valve 112 is opened. The whole cycle thenrepeats.

While the system of the invention is shown schematically, it wll bereadily understood by one skilled in the art that it can be easilyconstructed. The valves are all of a mechanical type which are camoperated so that a precise timed sequence of events can be carried outin a predetermined manner, the timing of the opening and closing of thevalves being controlled by the size, shape, configuration and speed atwhich the cams are moving.

The following "steps" are identifiable in the total reaction cycleinvolving gases and solids:

(1) Supply of the water vapor (steam) in the direction of flow.

(2) Diffusion of this steam into contact with the particulates ofmanganese oxides or to the reacting interface which may be on thesurface, or inside the particulate, depending on the oxidation level ofthat particular particulate in the gradient (overall).

(3) Interface reaction (intrinsic rate), including sequestering ofoxygen and the release of the gaseous product H₂.

(4) Diffusion of product from the interface.

(5) Removal of product, H₂, in the direction of flow.

(6) Concurrently with Steps 2-5, the water vapor is also being directlydissociated by photon action, producing both H₂ and H₂ O₂, as describedin detail below.

(7) Diffusion of combined oxygen from the interior of the reactant tothe interface, and then away from the reactant in the direction of flowof the H₂ and O₂ residual tailings.

(8) Combustion of the H₂ and O₂ tailings in the centrally locatedburner.

(9) Removal of products of combustion from the burner in its separatedirection of flow.

The instant process is a process in which a relatively small amount ofheat-energy input, (in the form of pre-heat for the reactant) providesconditions for the reactant to effect changes of state, during which agaseous chemical molecule is completely dissociated into its separategaseous atoms by two distinct phenomena. In the course of one of thesephenomena, the solid reactant concurrently effects a "change of state"by means of an exothermic transformation from one oxidation productlevel to another oxidation product level; and in the course of thesecond phenomena, to be described in detail below, the H₂ O moleculesare directly dissociated by photon energy, forming H₂ and also H₂ O₂,hydrogen peroxide.

It should also be noted that pressure changes play an important part inthe system. Specifically, the reactant is heated to a temperature wellabove the dissociation temperature for oxygen from the metallic oxide ofhigher oxidation number at room temperature. This temperature for MnO₂is given in handbooks as 535° C., and at atmospheric pressure this MnO₂will dissociate to Mn₂ O₃ at temperatures above 535° C. Accordingly, itis desired to operate at temperatures well above 535° C. such as 600° C.to 950° C. In addition, during the hydrogen formation portion of thecycle, the pressure must be well above atmospheric so that the oxygenwill be absorbed by the Mn₂ O₃ (the oxide of lower oxidation number),with a pressure of about at least 75 psi or 100 being preferred, andpreferably between 100 psi and 150 psi to as high as 200 psi or more. Inaddition, during the oxygen disproportionation phase, the free oxygenand other gases are removed from the vicinity of the reactant,preferably by a reduction in pressure to less than atmospheric, withabout one-tenth atmosphere being successfully employed. As can beappreciated, by using temperatures and pressures well above and belowcritical levels during the two phases of the cycle, increased speeds ofoperation may be obtained.

Reference is now made to FIGS. 2 and 3 wherein the heating means 20 isshown in more detail. Heating means 20, as already discussed, comprisesburner 70 and heat exchange coils 32, 38, 44, and 50. Burner 70comprises casing 128 made of any suitable metallic material lined with aporous fire brick insulation 130 which is carved or otherwise formed tofit casing 128 and has an axial hollow core running longitudinallythrough most of its length. The hollow core is, in turn, filled with asuitable surface catalyst 132 for "burning" hydrogen and oxygen to formsteam. Through the center of heating means 30 is a conventionalelectrical resistance heating element 140 which is used, when necessary,for pre-heating the system for a cold start. At the lower end of heatingmeans 20 as in the drawings, are atmospheric air inlet 104 and residualtailings inlet 114. At the upper end is exhaust line 68.

The next sub-system under consideration is the reaction chambers 12, 14,16 and 18. For an understanding of the construction of the reactionchambers, attention is directed to FIG. 4 where a single reactionchamber designated generally as 142 is shown. Reaction chamber 142comprises an outer casing 144 made of any suitable material such as 3/8"thick stainless steel or as discussed in the aforementioned co-pendingapplication. It is filled with reactant 126 as discussed above and asshown and described below in connection with FIGS. 8, 11 and 12. Passingaxially through the reactant is a conventional electrical resistanceheating element 146, this heater being essentially the same as heater140 in FIG. 22. This may be used for pre-heat in a cold start. Asalready discussed, however, the exact means used for pre-heating thesystem is not critical to the invention and any means well-known in theart for accomplishing this end may be used. The reactant 126, includingsensitizer and host materials, is placed in casing 144 leaving a spaceat each end, these spaces being designated in FIG. 23 as 148 and 150.Spaces 148 and 150 essentially serve the function of surge tanks,manifolds, or the like. Steam inlet 152 and vacuum inlet 154 areprovided at one end of reaction chamber 142 and hydrogen outlet 156 isprovided at the other end. Steam inlet 152 corresponds to conduit 56,for instance, vacuum outlet 154 corresponds to conduit 118, forinstance, and hydrogen outlet 156 corresponds to conduit 72, forinstance, in FIG. 1.

Turning now to FIG. 5, the preferred configuration of the apparatus isshown along with the sub-system which includes the valves and drivingmechanism for the same as well as the "plumbing". It will be seen thatthe valves which are described above are arrayed in a single line. Thevalves are of a conventional type which are operated by pushing orreleasing a plunger designated, for convenience of illustration, as 158in conjunction with valve 34. It will be appreciated that while thedescription of the valves refers to valve 34 and plunger 158 forexemplary purposes, each of the valves operates in the same manner. Avariable speed motor 160 turns a drive shaft 162 which is journaled inmounting plates 164 and 166. Fixedly mounted on drive shaft 162 are cams168, with one cam corresponding to each of the valves and mounted ondrive shaft 162 in such a way as to cooperate with plunger 158 of eachvalve. Thus, as motor 160 turns drive shaft 162 and, in turn, cams 168,the valves are opened and closed in a manner which is predetermined bythe positioning of cams 168. This, of course, will be readily understoodby one skilled in the art.

Referring further to FIG. 5, it will be seen that the reaction chambersare set vertically in an enclosure that is square in cross-section andare shown in the drawing with reaction chamber 12 in the front left-handcorner, reaction chamber 14 in the rear left-hand corner, reactionchamber 16 in the front right-hand corner, and reaction chamber 18 inthe rear right-hand corner. Heating means 20 is disposed in the center.The enclosure or, more specifically, inner enclosure 170 is preferablymade of magnesium oxide packed in a stainless steel container. Thismaterial was chosen because it distributes heat evenly throughout thevolume of the enclosure 170. Surrounding inner enclosure 170 is outerenclosure 172 which is made of any suitable material such as stainlesssteel and filled with a high quality insulation such as alumina fibers.It will be appreciated by one skilled in the art that any high quality,high temperature, insulating material may be used.

Returning to a consideration of the drawings, FIG. 6 is a blockschematic drawing showing in a central position the reaction chamber orchambers 202 and an immediately associated steam generator 204. Areservoir of water 206 supplies water to the steam generator 204, whichmay be of any of the types described in connection with earlier figuresof the drawings. In this connection, it may be noted that all of thearrangements shown in FIG. 6 are applicable to the hydrogen generationapparatus shown hereinabove in the present specification.

Steam or water vapor is supplied to the reaction chamber or chambers 202through line 208 which may of course be internally connected between theimmediately adjacent and thermally connected units 202 and 204. Hydrogenfrom reaction chamber or chambers 202 may be routed through output line210 to the venturi tube combining unit 212 which is also in intimateheat-conducting relationship with reaction chamber 202 and the streamgenerator 204. As mentioned above, in connection with manganese oxidethe temprature of the entire assembly, including the venturi unit 212,may be in the order of 600° to 950° C.

Hydrogen peroxide may be formed in either of two ways, and theproportion of hydrogen peroxide to hydrogen gas may be controlled byvalves 213 and 215. Initially, considering the formation of H₂ O₂ withinthe reactor chambers, by photon action, valving 215 would be openedwhile steam is present in the reaction chambers and while the H₂ gas isbeing drawn off, and oxygen at high pressure, corresponding to thepressure of the reaction chamber is admitted to chambers 202 via conduit217 from pump 219.

Now considering the subsequent formation of H₂ O₂, valve 215 would bepermanently closed, and valve 213 would be open. When hydrogen starts toflow rapidly through the Venturi unit 212 the check valve 214 will openand oxygen will be combined with hydrogen to form hydrogen peroxide. TheVenturi unit 212 is in intimate heat conducting relationship withreaction chamber 202 and during the preheat period, absorbs heat fromthe reaction chamber. Later, during operation, the combination ofhydrogen with oxygen is an exothermic reaction as set forthquantitatively in equation form hereinbelow, and supplies heat to thesystem. The hydrogen and hydrogen peroxide is stored in reservoir 216,which is maintained at a relatively high pressure level by the checkvalve 218 which prevents loss of hydrogen back toward the reactionchamber 202 between the intermitent withdrawing of hydrogen from thereaction chamber 202. Hydrogen and hydrogen peroxide may be withdrawn asneeded from the reservoir 216 through an output line 220. By closingboth valve 213 and valving 215, the amount of hydrogen peroxide which isgenerated is severely limited, and the bulk of the output will behydrogen, rather than H₂ O₂.

Vacuum pump 221 may be employed to speed up separation of oxygen,hydrogen tailings, and other residual gases from the reactant duringdissociation or disproportionation.

With regard to the block diagram of FIG. 6, it is to be understood thatthe components shown in this figure may be employed in connection withany system described hereinabove in the present specification.Specifically, the various input and output control valves have been, forthe most part, omitted from FIG. 6 for purposes of simplicity.Similarly, the precise physical arrangement, with the units 202, 204 and212, for example, being in intimate heat-conducting relationship witheach other, and insulated from the atmosphere, is not shown in FIG. 6,but may be in accordance with disclosures of other units disclosed inthe present specification.

FIG. 7 shows a typical pressure versus time cycle for a system inaccordance with the present invention using manganese oxide as thereactant, and four reaction chambers. This is, for example, of the typedescribed hereinabove in connection with FIGS. 1 through 5 of thedrawings.

The pressure is "gauge" pressure in pounds per square inch (psi). Withthis pressure scale, atmospheric pressure is of course indicated byzero.

Considering the cycles shown in FIG. 7 from an overall standpoint, thecomplete cycle for each reaction chamber including both breaking up thewater vapor and dissociating the oxygen from the reactant may be 40seconds. However, the cycles of the reaction chambers are evenlystaggered in operation, by 10 seconds in the example so that hydrogen isgenerated on a substantially continuous basis. In FIG. 7 the pressurecycle for reaction chamber No. 1 is shown in the lower characteristic,and the pressure cycle for reaction chamber No. 2 is shown in the uppercharacteristic. The pressure versus time characteristics for reactionchambers Nos. 3 and 4 are substantially the same as those of chambersNo. 1 and 2, but are displaced by additional 10 second intervals.

Now, referring specifically to the lower characteristic 230 in FIG. 7,the cycle starts with the opening of the water inlet valve for a coupleof seconds at the beginning of the cycle. Steam is promptly generatedand fills the first reaction chamber. At about 6 seconds, the hydrogenoutlet output valve is opened as indicated by arrow 232. Hydrogen and/orH₂ O₂ continues to flow until about 16 or 17 seconds of the cycle, whenthe hydrogen pressure drops to the hydrogen reservoir pressure,indicated as equal to 80 pounds by the dash dot line 234 in FIG. 7. Theclosure of the hydrogen reservoir check valve 218, as shown in FIG. 6,is indicated by the arrow 236 in FIG. 7. Soon after the closure of checkvalve 236 the pressure release and vacuum pump valve is opened, asindicated by arrow 238 and the pressure drops along characteristic 240to the negative pressure of about one-tenth of an atmosphere indicatedby line 242. During the interval from about 20 seconds to 40 seconds thedisproportionation phase takes place. Then at approximately 40 secondsthe water inlet valve is opened again, and the cycle repeats.

The upper characteristic in FIG. 7 shows the same cycle for reactionchamber No. 2 as described above for reaction chamber No. 1. In theupper characteristic the same reference numerals are employed, butprimes are employed in place of the unprimed numbers used in connectionwith the lower plot of FIG. 7.

FIG. 8 is a fragmentary view of a portion of a reaction chamber such asthat shown in FIGS. 1 and 4 described hereinabove. In FIG. 8 the outercylindrical wall 252 may for example be made of one-quarter orthree-eights inch stainless steel.

Referring more specifically to FIG. 8, in order to expose the manganeseoxide powder fully to the space within reaction chamber 258, thischamber is filled with a large number of hollow stainless steel screenelements which may be formed by taking small strips of stainless steeland folding them over upon themselves and welding or otherwise securingthem together to form a hollow enclosed space. The chamber 258 isinitially filled with these stainless steel, hollow mesh cells 260. Thena large quantity of manganese oxide is poured into the reaction chambersand is shaken down in among the stainless steel mesh cells to completelyfill the entire chamber 258. In FIG. 8 a number of these stainless steelmesh cells designated 560 are shown, and the manganese oxide powder 262between the cells is also indicated. It is to be understood, of course,that other techniques may be employed for exposing the reactant to thespace within the reaction chamber, but the foregoing system has provedeminently satisfactory in at least one 4-reaction chamber apparatuswhich has been successfully operated.

In addition, the host and sensitizer material may be included in thefabrication of the wire mesh cells 260. With waver vapor within thesewire mesh cells, this feedstock is fully exposed to the intenseradiation from the sensitizer.

FIG. 9 shows an improved structural arrangement of the reaction chambersin which the four reaction chambers 302, 304, 306 and 308 aredonut-shaped and are stacked up on top of one another in intimate heatconducting and transferring relationship. Each of the four reactionchambers is provided with two manifolds 310 and 312 to supply gases tothe reaction chambers and to remove gases therefrom. These input andoutput manifolds serve the same functions as the spaces 148 and 150 atthe top and bottom of the cylindrical reaction chambers as shown in FIG.4, for example.

Each of the reaction chambers 302, 304, 306, and 308 contain reactant,such as manganese oxide, and voids created by wire mesh cells asdescribed above, or other structure which will be described below, withwhich the sensitizer and host materials are associated.

A burner 314 extends through the central opening of all of the fourdonut-shaped reaction chambers. The burner 314 has the generalconfiguration shown in FIG. 3, but is provided with upper and lowerapertured plates 316 and 318 for ease in applying the hydrogen andoxygen to the burner and for ease of withdrawning the burned gaseousproducts from the unit. Although the details of the burner 314 are notshown, it includes the refractory lining and the granular refractorymaterial such as is shown at 130 and 132, respectively, in FIG. 3.

The unit of FIG. 9 is also provided with heavy upper and lower plates320 and 322, which are bolted together with a series of bolts 324 spacedaround the periphery of the plates 320 and 322. With this arrangementthe reaction chambers 302, 304, 306, and 308 are rigidly together inintimate heat conducting relationship, and can withstand very highpressures even at very high temperatures without deformation of thereaction chambers.

The reaction chamber assembly is mounted on any suitable insulatingsupport as indicated by the blocks 326. A lower metal base 328 andlighter gauge stainless steel metal sidewalls 330 are also provided.High temperature heat insulating ceramic wool encloses the reactionchamber assembly and reduces heat radiation to very low levels. Theceramic wool is indicated by reference numeral 332 in FIG. 9. Inpassing, it may be noted that the use of flat donut-shaped reactionchambers provides a geometry which is superior to the set of fivecylinders shown in FIG. 5, in that the reaction chambers are in moreintimate heat conducting association with one another and with thecentral burner, than in the arrangement of FIG. 5.

Apart from the physical arrangement of the four reaction chambers andthe central burner, the "plumbing" and mode of operation of the systemas described in connection with FIGS. 1 through 8, remains unchanged.

A more detailed consideraion of the absorption characteristic of watervapor and other possible feedstocks, and the matching of the host andsensitizer materials to the feedstock absorption characteristic will nowbe undertaken.

In FIG. 10 the relative transmittance and absorption of water vapor atdifferent wavelengths is shown. By way of example, note that atwavelengths of about 2.5 to 2.6 microns, the curve which representstransmittance has a dip designated 342 in FIG. 10. This is in contrastto the peaks 344 and 346 which are centered just above 2 microns, and inthe vicinity of 4 microns, respectively. A combined host material andsensitizer which will provide intense coherent radiation in the vicinityof 2.5 and 2.6 microns, and which absorbs energy in the vicinity of 1.2to 1.3 microns, will be employed as one set of materials forconcentrating energy and applying it to water vapor. The particular hostmaterial and sensitizer which provides this wavelength of absorbing heatenergy and radiating energy is calcium fluoride CaF₂ as the hostmaterial, and uranium-3 as the sensitizer.

Before considering FIGS. 11 and 12 some background relative to thephenomena which are taking place will now be included.

Initially, it may be noted that the theory of Masers and Lasers ofcourse forms a background for the present invention. The word "LASER" isan acronym which stands for the Light Amplification by the StimulatedEmission of Radiation. Although related to some extent to Maser andLaser theory, the present invention does not involve the intensecollimated beams of energy characteristic of Masers and Lasers; and ofcourse, Masers and Lasers do not derive their energy from a heatreservoir made up of a body of material at elevated temperatures.

Types of Radiation

There are two separate processes by which a material can become agenerator (or producer) or radiation energy after absorbing suitablequantities of primary energy. In the first process the absorbed energyis converted (degraded) into a low-quantum-energy heat that diffusesthrough the material which then emits radiation called thermalradiation.

In the second process an appreciable part of the absorbed energy istemporarily localized as relatively high-quantum-energy excitation ofatoms or small groups of atoms which then emit radiation calledluminescense radiation.

Specifically, "luminescence" is a process whereby matter generatesnonthermal radiation which is characteristic of the materials involvedand not the temperatures. Sometimes, however, the radiation as generatedis also called "luminescence". It is in fact luminescence only when theradiated energy is in excess of the thermal radiation produced by heat.

Thermal radiation from solids is generally a broad continuous spectrumof radiation, especially infrared, which is emitted in increasing amountas the temperature of the solid is increased.

The quality and quantity of thermal radiation depend almost exclusivelyon the temperature rather than the nature of the emitting solidmaterial. Broadly and objectively speaking, luminescence describesemission of radiaton (of subatomic origin) in excess of thermalradiation; that is, luminescence yields photon emission in excess of thephoton emission produced entirely by thermal agitation.

Luminescence is generally excited by primary photons or charged materialparticles having individual energies ranging from about 2 ev to over 10⁶ev and affords emitted photons with energies in excess of 1 ev. Whenluminescence is excited by energy liberated during chemical reactions,the liberated energy per emitting atom or molecule usually exceeds 1 ev.These excitation energies are hundreds to millions of times greater thanthe energies of individual phonons in solids. A single phonon canincrease the energy of an electron or atom in a solid by at most a fewhundredths of an electron volt, whereas the individual primary particlesnormally used to excite luminescence can provide energy increases up tothe total amount of energy carried by the primary particle (except forrest-mass energy), that is, tens to millions of electron volts.

In order to obtain barely visible emissions of thermal radiation from asolid, the temperature of the solid must be raised above 900° K. toobtain an appreciable probability of getting 1.7 ev (or greater)electronic excitations by the cumulative action of phonons.

The thermal radiations from real solids cannot exceed the emission whichwould be obtained from a perfect black body at the given temperature andfrequency. Most solids emit somewhat less thermal radiation than themaximum which is expressed by:

    P.sub.84 =[πhν.sup.3 C.sup.-3 (E.sup.hν/kT -1).sup.-1 erg cm.sup.-2 sec.sup.-1                                      (50)

The peak wavelength λpk of the broad emission band of black bodyradiation is inversely proportional to T, according to WIEN'Sdisplacement equation.

    λpk=0.29T.sup.-1 cm=2.7×10.sup.7 T.sup.-1 A   (51)

The TOTAL THERMAL EMISSIVE POWER P_(T) of a perfect black body increasesas T⁴, according to the STEFAN-BOLTZMANN LAW:

P_(T) =2 ⁵ k⁴ T⁴ /15C² h³ =5.7×10⁻⁵ T⁴ erg cm⁻² sec⁻¹ (52)

At room temperature (about 200° K.), λpk is in the far infrared at97,000 A, and P_(T) is only 4.6×10⁵ erg cm⁻² sec⁻¹, so that there is notan appreciable amount of radiation in the VISIBLE region between 4000and 7000 A.

At the temperature of an incandescent lamp filament (about 2800° K.),λpk is about 10,000 A, and P_(T) is 3.5×10⁹ erg cm⁻² sec⁻¹, so thatthere is an appreciable emission in the visible part of the spectrum. Inthe temperature range between about 700° and 1000° K. there is anoverlapping of feeble luminescence and feeble incandescence.

The present invention involves temperatures from a lower limit of about900° to 1000° Kelvin or about 600° to 700° Centigrade and ranges upwardfrom these temperatures with the upper limit controlled only by thestrengths of the materials utilized (1) as the reactant orhost/sensitizer, (2) for the reaction chamber, and (3) for the tanks,tubing, etc.

THE HASER CONCEPT

The Maser/Laser type of acronym may also be applied to another systemtermed "Haser", an acronym for "Heat Amplification by Stimulted Emissionof Radiation." As will be developed below, however, the term"Amplification" is not used in the sense of increasing signal strength,but in the sense of amplifying the effectiveness of heat energy.

The Haser application depends not as much on coherence ormonochromaticity per se, but rather on the unprecedented energy per unitarea. This radiated energy is a by-product of the coherence of theradiation, and can be many orders of magnitude greater in energy thannormal incoherent thermal radiation. To understand why this is possible,it is necessary to review briefly a few of the basic differences betweenthe incoherent radiation produced by an ordinary bright source and thecoherent light (radiation) produced by a laser or maser.

In a conventional source the atoms of a solid (or a gas) are agitatedeither thermally or electrically to higher energy states. When theseatoms return spontaneously to their lower levels, they radiate some oftheir excess energy as light. Since each atom behaves independently atthis state, its emission is at a random time and in a random directionwith a random polarization.

It follows that the light radiated in a single direction in the complexsum of all the light from the individual atoms. The phases of any twoatoms will tend to cancel their radiation in some directions and enhanceit in others. The total energy of the source will on the average beradiated uniformly in all accessible directions, and the amount ofenergy observed in a given direction will be proportional to the solidangle substituted by the observing device. In the Haser interior theobserving device is either a water-vapor molecule (or other feedstock)or another particulate of reactant.

The maximum total energy that can be radiated by a given source dependson two factors: the surface area of the source and the maximumtemperature to which the source has been heated. Therefore, in practice,the only way to increase the power output from an ordinary source beyondthe limitations imposed by the source material is to increase thesurface area of the source.

Power output, however, is only half the solution. Concentrated power ismuch more important than power itself. A 40-watt fluorescent lamp, forexample, produces more light than a 40-watt incandescent lamp, but thefluorescent lamp is not nearly as effective as the incandescent lightsource for a spotlight.

Now, in a laser or maser, the energy is also emitted when atoms dropfrom a higher energy level to a lower one; however, in this case theatoms are triggered and emit radiation (to a large percentage) inunison. In the case of the Haser, the atoms are triggered to emitradiation in unison by phonon/photon waves within the unit cavity orcell interior. Enough of the energy previously generated is retainedwithin the mass of particulates to maintain emission in a compatiblephase, polarization and direction. This phonon wave interacts with theexcited atoms and causes them (to a large degree) to emit their excessenergy in phase with the stimulating wave before they have a chance todo it randomly.

As a result, the Haser generates a good percentage of its radiatedenergy so that it travels in synchronism with the standing phonon waves,therefore concentrating the energy emitted as photons.

In effect, the radiated photons from the Haser particulates are allrelatively concentrated, monochromatic, and therefore, relativelycoherent energy sources. This results in an excellent energy densityeven though the photons are traveling in practically an infinite numberof directions, due to the fact that the particulate sources number inhundreds of millions. The photons moving from particulate to particulateimpact and are absorbed by other particulates. Then, this STORAGE,BUILD-UP, AND RELEASE of the "phase and amplitude of radiated energy,"combined with the fine particulate geometry of the Haser power (energy)source, which provides surface area to emit photons in extremes, allowsa "maximum efficiency utilization" of the radiated energy within theHaser cavity.

The act of controlling the spectral emissions to most effectivelydissociate (for example) water vapor, by sensitizing the host compoundproperly is another very important point. The monochromatic waves maybecome distorted in passing through substances, so that harmonic wavesare generated at two or more times their original frequency.

Infrared wavelengths may be converted into visible light, and visiblelight into ultraviolet waves.

This new system utilizes fine (small) particulates of solids comprisedof oxides which are predetermined by design within which some of thehost atoms are replaced by other frequency sensitive atoms alsopredetermined by design, which, provide stimulated absorption andemission at predetermined wavelengths.

An ohmic (or other) pre-heat provides to the heat reservoir mass theoriginal energy to liberate a massive volume of photons at the frequencyrange which will activate the sensitive atoms included in the hostcompound; the fine multi-faceted particulates absorb the photons whichnormally proceed as phonons through the particulate to generate andprovide large numbers of cavity resonances which stimulates emissionwith each internal excursion; therefore, again, the gain by thisregenerative amplifier when driven by the thermal noise fluctuationsfrom the cavity walls, can be significant.

In the case of the HASER, the principle emissions of radiation designedand produced to dissociate the chemical product may be emitted from thewoven wire mesh cavity balls or cells 260 (FIG. 8) that fill the entireHaser cavity.

The "preheat" energy can be electrical and inserted (through resistanceheaters) into the internal cavity or the heaters may also be external tothe cavity and heat the mass by conduction and radiation through solids.

Also, the "preheat" energy may be inserted by combusting suitable fuelssuch as hydrogen, hydrogen peroxide, alcohol, and other hydrocarbons,directly in the internal cavity of the unit or within a "center-core"burning unit as is designed into the unit of FIG. 9, for example.

As the reactive mass reaches temperature levels which excite themolecules and atoms to a radiating level of energy, phonons and photonsevolve which distribute the thermal energy within the mass.Incidentally, relative to the use of the terms "photon" and "phonon",when a photon traveling through space impinges on a solid, the resultantwave in the solid is termed a "phonon".

The ability of `atoms` to store energy has to do with the electronswithin the individual atoms. The electrons exist as a cloud of negativecharge around the positively charged nucleus. Each election occupies astate of energy and angular momentum that cannot be occupied by anyother election.

Therefore, the electrons tend to fill stable shells surrounding thenucleus.

The electrons of the outermost shell are the ones most easily affectedby outside forces because of their accessibility. These outer electronscan be moved to higher energy states, but they always tend to return totheir lowest energy state: the ground state. Electrons at certain levelsdecay (fall to a lower state) more easily than electrons at otherlevels.

Each excited electronic state of the atom has a characteristic lifetimethat indicates the average time it takes an electron to fall to a lowerlevel and therefore radiate a photon. Most excited states have lifetimesof about 10⁻⁸ second.

There are some excited states or levels in all atoms in which theelectron cannot decay easily by giving up a photon. Such atoms musttherefore wait for other means of giving up their energy, such ascolliding with other atoms or with the walls of the system. Electrons inthis state of energy tend to stay there for relatively long periods oftime (0.001 second or more), and are referred to as being in metastablestates. This is an important part of the storing of energy, which canthen be retrieved in the excitation process by stimulation.

the normal radiative decay from a higher electronic state to a lower oneis termed spontaneous emission. As discussed earlier, processes existthat can force an atomic electron to a higher state or stimulate it tojump to a lower state. An example of forcing, as discussed earlier, isprovided when a photon collides with an atom and excites the outerelectron to a higher level, which can happen when the energy orwavelength of the photon corresponds exactly to the difference in energybetween the state the electron is in and some higher possible state.This process is known as absorption because the photon (energy) isactually absorbed by the atom and all the photon's energy goes intoraising the electron to a higher state.

Similarly, as discussed earlier, the stimulated electron can move to alower level, provided that such a level exists and that the differencebetween the two levels corresponds to the energy of the incoming photonexactly. The energy given up by the electron in jumping to a lower stategoes into creating an additional photon with the same characteristics asthe colliding photon.

A large number of atoms can provide an increase in the radiated energyat the desired frequency or energy level, if the population of electronsin the excited states of the atoms is suitably arranged. Consider twoexcited levels of a system of identical atoms with the electrons dividedbetween the upper and lower levels. If a radiated photon having awavelength corresponding to the difference in energy between the twolevels is allowed to pass through the system medium, it will beamplified if there are more atoms with electrons in the upper state andabsorbed if there are more atoms with electrons in the lower state. Thecondition of having more atoms in the upper state is called a"population inversion"](because it goes against the normal processes ofnature, which tend to keep more electrons at lower energies than athigher energies).

The search for new Haser "systems" is therefore not easy, because one isworking against the natural tendencies of the electrons.

Another important consideration is the actual `lifetimes` of the ionenergy levels of the impurity atoms involved in the populationinversion. The upper level of a two-level system with a populationinversion radiates energy corresponding exactly to the differencebetween the two levels.

The electrons that have thus yielded energy by radiation, end up at thelower level. If they remained there, the situation would result whereinthere would be more atoms at the lower level than at the upper level,and as discussed earlier, there would be absorption instead of gain. Forcontinuous operation, one must find impurity atoms with combinations oflevels such that the lower level has a short lifetime and the upperlevel is preferentially populated. This necessity rules out the ionground state as a possible Haser level, since all ion ground states aremetastable. the pair (or more) of ion energy levels which will provideamplficiation must be energetically above the ground state but stillbelow the metastable states.

Although the original gas laser utilized electrical excitation ofelectronic transitions, later versions use vibrational transistions inmolecules such as carbon dioxide, and the excitation mechanism mayinvolve electrical or chemical excitation, or the burning of fuel. Inthe chemical laser, atomic species such as hydrogen and fluorine can bereacted to produce molecules in an excited vibrational state which inturn yields amplification or oscillation.

An entirely new excitation process was announced by Garry in 1970. Inthis, the gas dynamic laser, an appropriate fuel is burned to producecarbon dioxide and nitrogen at high temperature and pressure. Whenreleased through a nozzle into the optical resonator region, the gascools rapidly in terms of its kinetic or translational energy, but thepopulation of the vibrational energy levels of the carbon dioxidemolecules becomes inverted since the lower level of the laser transitionrelaxes more rapidly. In addition, the vibrationally excited nitrogenmolecules are in near resonance with the upper laser state of the carbondioxide and transfer energy with high efficiency to maintain theinversion. This type of `laser` has produced continuous powers as highas 60 kw.

The HASER phenomenon as utilized in the present invention, actually usesa thermochemical excitation mechanism. The original preheat energyprepares the reactant material within the reaction chamber by bringingthe material to photon emitting temperatures.

When water vapor is introduced into the chamber of FIGS. 1 and 8, forexample, the excited billions of photons emitted and traveling betweenparticulates, strikes the sensitized "Cvities" with a barrage of photonsdesigned to provide frequency, amplitude, and steric factor impactadequate to dissociate the H₂ O molecules. On dissociation, the 2H₂, andO₂ molecules are vibrating at very high temperatures and pressures whichare compatible with recombining these molecules through the "activatedcomplex" mechanism into their (high temperature) preferential H₂O.sub. + H₂ molecules, w hich incidentally evolves more than 33KCal/mole heat energy. As the steam enters and traverses the cavity, anamount of the steam (depending upon the design of the contents of thereactor chamber and the relative amount of reactant, manganese oxide orother similar metal oxide, and the host/sensitizer material), combineswith the reactant, which raises the oxidation level through the processof oxidation; and this of course, evolves heat energy (because this isan exothemic reaction), which, broadcasts more photons of energythroughout the cavity interior, to react with the sensitizers andactivators; and this in turn creates massive amounts of new photons ofenergy to dissociate the H₂ O vapor and maintain the reactiontemperatures within the host materials.

HASER CAVITIES

Referring again to FIG. 8, the cavities 260 can be fabricated of veryfine mesh woven wire, which is cut into small sections, stamped, folded,and the outer edges of the wire mesh are secured together to form ahollow cell. The wire, of a diameter approximately equal to 0.002 inch,is made up of the elements, compounds, and a metal carrier (inert to theprocess), and is initially woven and formed into the cells as describedabove. It is then transformed into the desired host and sensitizermaterials through oxidation in an atmospherically controlled furnace orkiln.

CERAMIC HASER TUBES

Instead of the wire mesh cells 260 as shown in FIG. 8, the preferredform of Haser cavity is shown in FIG. 11 in which a large number ofceramic tubes 352 are present. These tubes are preferably extruded frommullite, which is a common clay having the approximate chemicalstructure of 2Al₂ O₃ . SiO₂ with a range to 3Al₂ O₃ . 2SiO₂. Suitablequantities of host and sensitizer materials, as described below, areadded to, and thoroughly mixed with the mullite prior to extrusion.Subsequent to extrusion the tubes are fired in a suitable kiln orfurnace. The tubes may suitably have a diameter of about 1/4 inch or 1/2inch and be from 1 to 12 inches in length. The sidewalls may suitably befrom 1/32 to 1/16 of an inch in thickness, but none of the foregoingdimensions are critical. After firing, the tubes 352 are provided withfilters 354 in both ends. The filters may be of any suitable structure,for example, several layers of metal gauze, to prevent the intrusion ofthe reactant 356 which may, for example, be manganese oxide. In practicethe ceramic tubes 352 with their associated filters 354 may be initiallyplaced in one of the reaction chambers such as reaction chamber 302,304, 306, and 308 of FIG. 9, or the chambers 126 of FIG. 1; and thenpowdered metallic manganese or manganese oxide may be poured in and theentire unit vibrated until the manganese oxide 356 as shown in FIG. 11fills all the space around the ceramic tubes 352. With this arrangement,of course, the water vapor is present within all of the ceramic tubes352; heat is provided by the manganese oxide 356; and radiation from thehost/sensitizer combination forming part of the ceramic walls 352radiates intense coherent energy in one or more of the absorption bandsof water vapor; and this intense radiation serves to dissociate thehydrogen and oxygen atoms making up the water vapor molecule.

The foregoing action is shown diagrammatically in FIG. 12 in which thetube 352 is shown centrally located and the surrounding particles ofmanganese oxide 356 are shown radiating broad spectrum thermal radiation358 in all directions including into the ceramic tube 352. The watervapor particles 360 shown as small circles within the tube 352 may bedirectly impacted by the coherent radiation 362 which is emitted by thehost/sensitizer combination included in the walls of ceramic tubes 352.It may be noted, that for convenience in illustration, the magnaneseoxide particles are shown spaced apart in FIG. 12; however, in practicethey would be filling all of the space within the reaction chamberswhich is not filled with the ceramic tubes 352.

HOST/SENSITIZERS FOR WATER VAPOR FEEDSTOCK

In the tabulation which will be set forth below, suitable host materialsand sensitizers for applying radiation to water vapor will be set forth.In this tabulation the chemical symbols for the elements will beemployed, and the host material will be listed first followed by thesensitizer material. In each case the absorption band for the hostmaterial will initially be given and then the emission wavelength of thesensitizer will be sent forth. Following the tabulation, the absorptioncharacteristic of water vapor as shown in FIG. 10 wll be reviewed andthe relationship of the emisson lines of the sensitizers to theabsorption bands of the water vapor will be discussed.

    ______________________________________                                        (a) Ca WO.sub.4 : Nd.sup.3+ Where                                                 Absorption = 0.74 microns-0.76 microns                                                                Ca,(Calcium)                                          Emission = 1.065 microns                                                                              W,(Tungsten)                                                                  Nd,(Neodymium)                                    (b) Ca WO.sub.4 : Nd.sup.3+                                                       Absorption = 0.87 microns-0.89 microns                                                                (Same)                                                Emission = 1.3372 microns                                                 (c) Y.sub.3 Al.sub.5 O.sub.12 : Er.sup.3+                                                                 Where                                                 Absorption = 0.46 microns-0.47 microns                                                                Y,(Yttrium)                                           Emission = 1.6602 microns                                                                             Al, (Aluminum)                                                                Er,(Erbium)                                       (d) Y.sub.3 Al.sub.5 O.sub.12 : Er.sup.3+                                         Absorption = 0.52 microns-0.54 microns                                                                (Same)                                            (e) CaF.sub.2 : U.sup.3+    Where                                                 Absorption = 1.2 = microns-1.3 microns                                                                Ca,(Calcium)                                          Emission = 2.5111 microns-2.613                                                                       F(Fluorine)                                           microns                 U(Uranium)                                        ______________________________________                                    

In the foregoing tabulation it may be noted that there are only threeseparate combinations of host and sensitizer materials which are beingemployed. More specifically, the combination of calcium tungstate andneodymium produce output radiations both at 1.065 microns and also at1.3372 microns as set forth in examples (a) and (b). It may be notedthat the absorption wavelengths for the two output emissions differcorrespondingly. The combination tabulated in examples (c) and 8d) setforth above include yttrium aluminum oxide as the host material anderbium as the sensitizer. In this case, the emitted radiation for both(c) and (d) is at 1.6602 microns; however, the absorption for the twoexamples is at different frequencies. The final example (e) usingcalcium fluoride as the host material and uranium-3 as the sensitizerwas mentioned above

With regard to the matching of the emitted radiation from thesensitizers with the absorption bands shown in FIG. 10 for water vaporas a feedstock, the high absorption band for water vapor extending fromabout 2.4 microns to about 3.1 microns is well located to receiveemitted energy in the 2.5 microns to 2.6 micron wavelength region fromexample (e) tabulated above. With regard to examples (a) through (d), acursory review of the emission wavelengths and the correspondingmoderately sharp absorption bands between 1 and 2 microns would indicatethat there is not necessarily an exact correspondence. However, it hasbeen determined that there is a certain amount of broadening of theradiation and of the absorption characteristics which occurs at hightemperatures; accordingly, with the basic location of the emission linesand the absorption points as indicated in the above table and in FIG.10, the practical result is good coupling from the emitted radiation tothe water vapor molecules at the 1,000 °Kelvin temperature at which thesystem is operative.

With regard to the relative quantities of the host and sensitizermaterial in the mullite, the quantity of host material should beapproximately 25 to 1,000 times greater than the amount of associatedsensitizer material. A ratio is approximately 0.5% of sensitizer of theamount of host material is the general order of magnitude which shouldbe employed. In addition, the quantity of each particular category ofhost and sensitizer material such as those set forth in the tabulationof combinations (a) through (e) set forth above, should be proportionedto the absorption bands of the feedstock which is being irradiated.Thus, in the particular example under consideration, where thehost/sensitizer combination (e) using calcium fluoride and uranium-3, ismatched to a broad absorption band of water vapor, a larger quantity ofthis host/sensitizer combination should be employed as compared withcombination (a), (b) and combination (c), (d). Thus, in the making ofthe ceramic tubes, the material which is being prepared might includeapproximately 88% by weight of mullite, 8% by weight of thehost/sensitizer combination (e), and 2% by weight of each ofhost/sensitizer combinations (a), (b) and (c), (d). Similarly, in theevent that the wire mesh is employed, the host sensitizer/sensitizercombinations may be added in the same proportions to stainless steelwire and the combination material drawn into wires and formed into mesh.Alternatively, after the preparation of the stainless steel wire cells,mullite together with the host sensitizer combinations could be appliedin several bands in the plastic state around the stainless steel wiremesh cells, and then fired, to produce the desired result. This result,as mentioned above, involves the provision of spaces throughout a bodyof material constituting a heat reservoir, and locating host/sensitizercombinations around the boundaries of these spaces or voids in thematerial.

The chemical formula for mullite was given above, and it is again notedthat mullite includes aluminum oxide Al₂ O₃ and silicon dioxide SiO₂ incertain proportions noted above. In order to enhance the "HASER" actionand increase the energization of the host/sensitizer combinations (a)through (e) set forth above, a material such as chromium, which acts asa sensitizer in cooperation with the aluminum oxide in mullite whichacts as the host material. The chromium-aluminum oxide, sensitizer-hostcombination produces strong output radiation at a number of wavelengths,including output radiation centered at 0.6934 microns, when the Al₂ O₃is absorbing energy at 0.5 microns. The radiation centered at 0.6934 isbroadened at the high operating conditions so that the radiation extendsfrom 0.6 or 0.65 to 0.75 or 0.8 microns, thus providing supplementalinput energy to example (a) set forth hereinabove, which involvesabsorption at about 0.74 to 0.76 microns. The Al₂ O₃ /Cr combination mayalso directly apply energy to the feedstock when the output radiation isof the proper frequency and may also pump other host/sensitizercombinations. When chromium is used it will be present in quantities inthe order of five per cent by weight or less of the mullite employed asthe basic material of the tubes 352 as shown in FIGS. 11 and 12.

MATERIAL REQUIREMENTS

The primary requirements for potential solid-state Maser/Haser materialsare, first, that the composition should fluoresce with a suitably highintensity at elevated temperatures by means of thermal energy alone and,second, that the matrix should be transparent or has no absorptiontransition at the operation frequency; it should also be chemicallystable and have no caustic characteristic.

Preferably, the terminal level of the Haser transition of the active ionshould be far enough above the ground state so that three or four-leveloperation is possible and at elevated temperatures.

The lifetime of the metastable level from which the Haser transitionoriginates should be, insofar as possible, equal to the lifetime forspontaneous emission with no constraints imposed by competitivedissipation to the matrix. In four-level operation of the lifetime ofthe terminal level of the transition must be smaller than that of themetastable level; otherwise, a suitable excess population in the upperlevel cannot be maintained.

This condition is generally obtained when the terminal level lies in thephonon absorption region, preferably between 6000 and 19,000 cm⁻¹. Inaddition, it is helpful for the excited active ion to be unable toabsorb photons corresponding in energy to the Haser transition. Wheresuch absorption into a higher level or band is possible, thephoton/phonon flux in the particulate cavity is reduced and themetastable level depleted.

For best coherence the active ions should occupy equivalent positions inthe host structure, so that there will not be a multiplicity of spectra.When these ions are in completely unique sites, the emission spectrumhas the minimum detail and line width consistent with the site symmetry,the crystal field, and the active-ion concentration. In general, thehigher the site symmetry the more degenerate the electronic states ofthe active ion. Therefore, fewer distinct transitions should be observedin fluorescence and, on the average, each emission transition shouldflouresce a greater portion of the absorbed energy. However, there arealso fewer distinct absorption transitions, and certain emissiontransitions may be favored in a low-symmetry environment. As long as theemission transitions are few in number, the low symmetry environment mayprove to be advantageous by virtue of a broader absorption coverage.

Different classes of active ions seldom find optimum environments in thesame host structure. Different activator ions are best accommodated inoxides or fluorides, where the cations of the matrix are approximatelyequal in size to the activator. Al₂ O₃, MgO, MgFl₂, and ZnF₂ are typicalmatrices for transition-metal ions, CaF₂ is particularly useful fordivalent rare-earth ions, and CaWO₄, LaF₃, and Y₂ O₃ are best suited fortrivalent rare-earth ions for lasers. Y₃ Al₅ O₁₂ can readily accommodateboth trivalent rare-earth ions and trivalent 3d transition-metal ions.Certain crystals have conveniently disposed matrix absorption bands andthese can be used to absorb pumped radiation over a broad spectrum.

The excitation may be subsequently transferred to trivalent rare-earthions contained in the matrix and therefore, greatly enhance the overallefficiency of fluorescence. It probable is essential to move into thevisible region, to obtain continuous operation for molybdates orniobates.

In comparison, materials which have their matrix absorption edges wellabove the excitation range but absorb strongly as a result of the activeions having strong absorption bands of their own, together with narrowemission lines, can afford very favorable pumping conditions.

Ions such as, Cr³⁺, Chromium, and. Dy²⁺, Dysprosium offer thisadvantage.

The past decade has provided rapid extension of spectral measurementsand theoretical analysis, such that the properties of most of thedivalent and trivalent activator species are well understood. Theinterest in solid-state masers and lasers, has motivated the preparationof various crystals containing divalent rare-earth ion species and theextensive study of their infrared characteristics. Parallel studies ofthe infrared properties of the transition-metal ions and trivalentrare-earth ions have been equally productive.

The selection of materials for Hasers which will operate in the infraredregion depends on the disposition of the vibrational bands in thematrices. Because vibrational levels may drain an electronic state, theyshould not be too close below the metastable level, or the latter shouldlie below the vibrational levels in energy.

Suitable coupled pairs which provide a mutual cross relacation can alsobe used advantageously to minimize loss of efficiency due tofluorescence from levels lying higher than the metastable level ofinterest and loss to the phonon spectrum. It is also desirable toincrease the efficiencies of masers that terminate on phonon levels.This mechanism of operation offers the possibility of a maser that canbe tuned over a broad range of frequencies.

PREFERRED LATTICES

Oxygen-dominated compounds are those in which oxygen is a major chemicalconstituent of the host lattice. They may be classified according totheir chemical composition into four groups.

The first group, comprising the simplest compounds, has the genericformula M_(x) O_(y), representative numbers being the alkaline earthoxides and Al₂ O₃, Y₂ O₃, and ThO₂, with Cr³⁺, Mn²⁺, and the rare earthsas common activators. Other compounds included in the generic formulaare CuO, and ZnS and the other II-VI wide-band-gap compounds.

The second and largest group are the binary oxides, M_(x) A_(y) O_(z),where M is any element of Group II, A or B, and Period 2 to 6, and A isTi, Zr, V, Nb, Mo, B, Al, Si, Ge, P, As, Sb, or S.

In many cases x=4y, the oxygens nearly tetrahedrally arranged arond themultivalent atom, A.

The common activators are Mn²⁺, Mn⁴⁺, Ag⁺, Sn²⁺, Tl⁺, Pb²⁺, and the rareearths. Included in this group also are the wwell-known self-activatedcompounds comprised of tungstates and molybdates, which are commonlycalled scheelites (although some do not have the scheelite structure).These require no activating impurity, because the energy transitionstake place within the anion, although impurity-activated luminescence isalso observed.

Of the impurity-activated members of the binary oxides, the borates,phosphates and silicates are the most numerous.

Ternary systems, M_(x) A_(y) B_(y) O_(z), constitute the third category.M and A and B are the elements listed in the binary systems plus thealkali metals.

The most common activators, other than the rare earths, are those listedwith the binary oxides. There are a few ternary compounds not containingtungsten or molybdenum which are believed to be self-activated.

There are many other oxygen-containing inorganic luminescent solids,including a large number of rare-earth salts and impurity-activatednitrites, carbonates, etc. The work on the latter is largely incomplete.The work on the rare-earth salts constitutes a well-studied separatediscipline (Diecke et al, 1961).

Considering the small number of possible combinations of simple oxidesand activators, it is surprising that new prospects in this groupcontinue to be found. New compounds, however, consisting of oxides ofantimony, germanium, thorium, calcium, strontium, yttrium, andgadolinium with various activators have been developed over the last fewyears.

The valence of manganese in phosphors or compounds is interestingbecause of its use as an activator in many lattices. Kroger (1948)showed that the broad structureless red or green emission spectra ofmanganese-activated compounds is generally due to Mn²⁺, whereas the rednarrow-banded emission is due to Mn⁴⁺

SUMMARY

In the same way that the spectroscopy of atoms provided basicinformation on atomic structure, careful study of controlledluminescence of solids provide information on band structures and energylevels of impurities and imperfections. In some cases, the spectra ofimpurities yield, through the application of crystal field theory,information on the symmetry and strength of the crystal field at theimpurity site. The absorption or excitation spectra involve electronicstates of the system with equilibrium nuclear coordinates characteristicof the ground state; luminescent emission spectra involves electronicstates with the equilibrium nuclear coordinates of the emitting state.

Additionally, detailed theoretical knowledge of band structure and ofimpurities and imperfections obtained from semiconductor andphotoconductor research provides understanding of the luminescence ofthese materials.

Luminescence is generally investigated as a steady-state phenomenon,wherein the compound interacts with the excitation source and emitsradiated energy continuously. The thermodynamic parameters of thecompound remain time independent at every point in the system, despitethe occurrence of excitation, emission, and dissipative processes.

Irreversible thermodynamics is concerned with just such open systems,which interact with their environment in a stationary way.

It is a principle of irreversible thermodynamics that the entropyproduction is positive in every macroscopic region of the systemundergoing irreversible processes.

Macroscopic regions refer to regions large enough for microscopicfluctuations to exist but small enough for approximate equilibrium toexit within each region. We are especially interested in the morecomplex excitation mechanisms involving energy transfer betweendifferent macroscopic regions not in equilibrium with each other.

LIGHT ABSORPTION AND COLOR

An electromatic radiation, (such as radiowave, light, and X-ray) can becharacterized by its particular wavelength, LAMBDA, λ (measured in cm orA), or by its wave number, ^(NU), ν (the reciprocal of thewavelength),ν=1/λ, commonly expressed in reciprocal centimeters, cm⁻¹.

Each unit of radiation (a photon) corresponds to a quantum of radiantenergy, E, which is directly proportional to the wave number, ν. Sincechemical calculations are founded on a mole basis, in discussing therelationship between radiant energy and chemical processes (responsiveactivators and hosts) it is convenient to express radiant energy inkcal/mole of photons. We can do so with this accepted relationship: theradiant energy in 1 mole of photons, with ν=350 cm⁻¹, is equal to 1kcal.

Therefore, we can obtain the energy (expressed in kcal/mole) for photonsof a given wave number simply by multiplying the value of ν expressed incm⁻¹ by the conversion factor ##EQU1##

For example, the energy of light photons with ν=20,000 cm⁻¹ is: ##EQU2##and the energy of a single photon of ν=20,000 cm⁻¹ is: ##EQU3##

The wave number, and the energy, of electromagnetic radiations varieswithin an extremely wide range --ν=10¹⁴ cm⁻¹ for the γ-rays emitted innuclear reactions to ν=10⁻⁶ cm⁻¹ for radiowaves. In between these twoextremes, there is a continuum of radiations of intermediate wavenumbers--the "visible region", which extends approximately from 27,000cm⁻¹ to 13,500 cm⁻¹.

In general, when white light strikes a substance, part of the light isabsorbed and part is transmitted (if the substance is transparent) orpart is reflected (if the substance is opaque). A substance may absorbpreferentially the light photons of one (or more) region(s) of thespectrum, so that the transmitted light or the reflected light isrelatively richer in the radiations of the remaining regions.

The combined effect of these remaining radiations is observed as aparticular color (when it is in the visible spectrum)

For example, a substance that, when exposed to white light, absorbsalmost all photons in the entire yellow-to-violet region (say from17,000 to 27,000 cm⁻¹) will "appear red", because only the radiations inthe red region of the spectrum (13,500 to about 17,000 cm⁻¹), which arenot absorbed, remain to be observed.

Similarly, a substance that "appears yellow" absorbs photons of both thegreen-to-violet region (from 19,000 cm⁻¹ to 27,000 cm⁻¹) and the redregion (from 13,500 to 16,000 cm⁻¹) of the visible spectrum.

Since light (radiation) is energy, the absorption of radiation isabsorption of energy; it is well known, that, if a substance absorbslight, the corresponding absorbed energy may be used to promote certainatoms, ions, or molecules of a substance from "ground-state" to an"excited state". For example, an atom, ion, or molecule which absorbs aphoton of a given wave number takes on a `quantum` of energy that mayserve to promote one electron from a lower energy orbital to a higher(available) energy orbital. In general, different electronic transitionsinvolve the absorption of different quanta of energy.

HASER DESIGN CONSIDERATIONS

Some of the factors which are involved in the design of Haser apparatusinclude the following:

(a) Thermally isolated chamber.

(b) Sensitizers-activators responsive to input heatenergy frequencies.

(c) Design amounts of "impurity" sensitizers required.

(d) Design the host solid while considering the following:

(1.) Lattice Vibrations

(1.1) Geometry of crystalline solids.

(1.2) Crystal lattice and reciprocal lattice. p1 (1.3) Brillouin zoneand g-space.

(1.4) Lattice vibrations of an infinite crystal with one atom per unitcell.

(1.5) Lattice vibrations of a finite crystal with one atoms per unitcell.

(1.6) Lattice vibrations of a crystal with more than one atom per unitcell.

(2.) Thermodynamics of Phonons

(2.1) Density matrix of an ensemble

(2.2) Internal energy of a phonon gas.

(2.3) Einstein and Debye approximations of the density of (A) phononstates.

(2.4) Phonons and photons: similarities and differences.

(3.) Ion-Photon Interaction: Absorption and Emission of Radiation

(3.1) Ion-radiation interaction.

(3.2) Expansion of the interaction hamiltonia Different types ofradiation.

(3.3) Density of final states

(3.4) Transition probability per unit time.

(3.5) Dipole radiation.

(3.6) Selection rules for radiative transiting

(3.7) Selection rules for transitions between eigenstates of angularmomentum.

(3.8) Selection rules for atomic systems.

(3.9) Electric dipole radiation.

(3.10) Magnetic dipole radiation.

(3.11) Electric quadrupole radiation.

(3.12) Selection rules for ions in crystals.

(3.13) Intensities of radiative transitions

(4.) Ion-Vibration Interaction: Radiationless Processes, Thermal Shift,and Broadening of Sharp Spectral Lines

(4.1) Ion-vibration interaction.

(4.2) Radiationless processes in a crystal absorption and emission of aphonon.

(4.3) Raman processes.

(4.4) Orbach processes.

(4.5) Multiphonon processes.

(4.6) Line broadening mechanisms

(4.7) Probability densities and superposition of probability densities:Voigt profile

(4.8) Thermal broadening of sharp lines.

(4.9) Raman scattering of phonons

(5.) Vibrational-Electronic Interaction

(5.1) Ion-vibration interaction in molecular complexes.

(5.2) Vibronic spectra of molecular complexes

(5.3) Vibronic lines in absorption.

(5.4) Selection rules for vibronic processes.

(5.5) Space groups and lattice vibrations.

(5.6) Normal modes of vibrations in crystals.

(5.7) Lattice absorption in perfect crystals.

(5.8) Phonon activation due to impurity ions in crystals.

(5.9) Selection rules for vibronic transitions due to magneticimpurities in crystals.

SPECIFIC EXAMPLES

Some underlying principles involved in the selection of Haser systemshave been set out hereinabove and a preferred embodiment has beendescribed which involves water vapor as a feedstock and the generationof hydrogen and/or hydrogen peroxide. It is to be understood that theHaser concept is not limited to the specific embodiment described hereinbut has more general applicability in the conversion of broad spectrumheat energy or radiation to particular frequencies which lie within theabsorption band or bands of any selected feedstock.

The feedstock may be gaseous or liquid or even a slurry, and may bebrought into proximity with the heat reservoir and associated host andsensitizer material in any desired and practical manner. The heat in theheat reservoir may be generated in any suitable manner including the useof the exothermic reactor for generating hydrogen and hydrogen peroxideand/or the combustion of the hydrogen and hydrogen peroxide.

The feedstock may for example be directed through the heat reservoir bya pipe suitable coiled to provide for adequate exposure to theradiation. The pipe may be transparent to the radiation being applied tothe feedstock; or alternatively, the pipe may be made of materialcontaining the specially selected host and sensitizer material.

In the following examples, a number of reactions are set forth and theseare followed by an identification of a host and sensitizer materialwhich will concentrate the broader spectrum heat energy to one of theabsorption bands of the feedstock. Incidentally, in the followingexamples, in addition to the standard symbols for the elements, thefollowing abbreviations are used: Et for ethyl, C₂ H₅ ; Ph for phenyl,C₆ H₅ ; Pr for propyl, C₃ H₇ ; and Bu for butyl, C₄ H₉. In addition tothe host and sensitizers shown in each of the following examples, Al₂ O₃in mullite and Cr +3 may advantageously be used (absorption at 0.5microns; emission centered at 0.6934 microns). As noted above, themullite may conveniently be employed to physically support the host andsensitizer materials. The actual examples follow:

Example No. 1

    ______________________________________                                        B.sub.2 H, Et.sub.2 O (solution) →                                     HYDROBENZOIN, ISOHYDROBENZOIN = (Reaction)                                    ______________________________________                                        Al.sub.2 O.sub.3 (mallite) : Cr.sup.3+                                                          Sr F.sub.2 : Sm.sup.2+                                      Absorption = 0.5 microns                                                                        Absorption = 0.58-0.68 micron                               Emission = 0.6934 ± 0.1 micron                                                               Emission = 0.6967 micron                                    ______________________________________                                    

Example No. 2

    ______________________________________                                        AcH,NH.sub.3,HCN(aq.) → C.sub.6 H.sub.12 O.sub.3 N.sub.2 =             (Reaction)                                                                    ______________________________________                                                LaP.sub.3 : Pr.sup.3+                                                         Absorption = 0.43-0.48 micron                                                 Emission = 0.5985 micron                                              ______________________________________                                    

Example No. 3

    ______________________________________                                        PARALDEHYDE, O.sub.2 → H.sub.2 O.sub.2 = (Reaction)                    ______________________________________                                                Ca F.sub.2 : Sm.sup.2+                                                        Absorption = 0.4-0.45 micron                                                  Emission = 0.7085 micron                                              ______________________________________                                    

Example No. 4

    ______________________________________                                        HCHO, FeCl.sub.5 (aq.) → FeCl.sub.2, HCO.sub.2 H, HCL                  = (reaction)                                                                  (glycolaldehyde)                                                              ______________________________________                                                Y.sub.2 O.sub.3 : Eu.sup.3+                                                   Absorption = 0.2-0.28 micron                                                  Emission = 0.6113 micron                                              ______________________________________                                    

Example No. 5

    ______________________________________                                        B.sub.2 H, AROMATIC KETONES → POLYMERS, other KETONES,                 BENZOATES = (Reaction)                                                        ______________________________________                                                 Y.sub.3 Al.sub.5 O.sub.12 : Yb.sup.3+                                        Absorption = 0.9-1.0 microns                                                  Emission = 1.01 microns                                               ______________________________________                                    

Example No. 6

    ______________________________________                                        B.sub.2 H, PhNO.sub.2 →                                                B.sub.2 OH, SEVERAL NITROGEN COMPOUNDS = (Reaction)                           ______________________________________                                                 Nd.sup.3+ : Cr.sup.3+                                                         Absorption = 0.5 micron                                                       Emission = 1.0612 microns                                            ______________________________________                                    

Example No. 7

    ______________________________________                                        Me.sub.2 CO,Et.sub.2 O (solution) → 150 - PROPYL ALCOHOL,              ADDITIONAL COMPOUNDS = (Reaction)                                             ______________________________________                                                Ca WO.sub.4 : Nd.sup.3+                                                       Absorption = 0.57-0.60 micron                                                 Emission = 0.9145 micron                                              ______________________________________                                    

Example No.8

    ______________________________________                                        CYCLOHEXANONE → CAPROIC ACID,                                          RESIN, ALDEHYDE = (Reaction)                                                  ______________________________________                                                CaF.sub.2 : Tm.sup.3+                                                         Absorption = 0.39-0.46 micron                                                 Emission = 1.116 microns                                              ______________________________________                                    

Example No. 9

    ______________________________________                                        CARVONE, EtOH (aq.) → KETONE RESEMBLING                                CAMPHOR, RESIN =(Reaction)                                                    ______________________________________                                                Ca WO.sub.4 : Pr.sup.3+                                                       Absorption =0.43-0.49 micron                                                  Emission =1.0468 microns                                              ______________________________________                                    

Example No. 10

    ______________________________________                                        CAMPHOR, EtOH (aq.) → CAMPHOLENIC ACID,                                = (Reaction) AcH,C.sub.10 H.sub.16 O                                          ______________________________________                                        Ca F.sub.2 : Dy.sup.2+  : Sm.sup.2+                                           Absorption = 0.58-0.68 } 0.8-1.0 micron                                       Emission = 0.6967 micron                                                      2.36 microns                                                                  ______________________________________                                    

Example No. 11

    ______________________________________                                        COUMARIN, EtOH, PARALDEHYDE, → HYDRO -                                 DI - COUMARIN or C.sub.6 H.sub.6 (solution)   = (Reaction)                    ______________________________________                                               CaWO.sub.4 : Nd.sup.3+ : Ho.sup.3+                                            Absorption = 0.57-0.6 0.74-0.76                                               0.44-0.46 micron                                                              Emission = 0.9145 micron                                                      1.065 microns                                                                 2.046 microns                                                          ______________________________________                                    

Example No. 12

    ______________________________________                                        BENZOIN, EtOH (solution) → HYDROBENZOIN, AcH.sub.3,                    ISOFORM RESIN   = (Reaction)                                                  ______________________________________                                                 Y.sub.2 O.sub.3 : Eu.sup.3+                                                   Absorption = 0.87 micron                                                      Emission = 0.6113 micron                                             ______________________________________                                    

Example No. 13

    ______________________________________                                        QUINONE, Et.sub.2 O (solution) → HYDROQUINONE, RESINS                  = (Reaction)                                                                  ______________________________________                                        Same Host/Sensitizer; Absorption; and Emission as                             Nos. 1, 3 and 4                                                               ______________________________________                                    

Example No. 14

    ______________________________________                                        THYMOQUINONE, Et.sub.2 O (solution) → POLYMER                          (POLYTHYMOQUINONE)   = (Reaction)                                             ______________________________________                                        Same Host/Sensitizer; Absorption; and Emission as                             Nos. 1 and 3                                                                  ______________________________________                                    

Example No. 15

    ______________________________________                                        4 - Me QUINOLINE → RESIN, ALKALI SOLUBLE                               PRODUCT   = (Reaction)                                                        ______________________________________                                        Same Host/Sensitizer; Absorption; and Emission as                             Nos. 5, 6, and 8                                                              ______________________________________                                    

FIG. 13 is a schematic showing of an apparatus for a continuouslyprocessing feed stock such as the materials disclosed in the foregoingexamples, or steam, of course. In FIG. 13 the reaction chamber 402 isprovided with upper and lower manifold chambers 404 and 406 which areseparated from the main portion of the reaction chamber 402 by aperturedplates 408 and 410. Within the reaction chamber 402 are a large numberof the ceramic tubes 412 such as those shown in FIG. 11. All of thespace within chamber 402 apart from that occupied by the tubes 354 isfilled with a reactant such as manganese oxide or other reactantsdisclosed elsewhere in the present case and in my prior co-pendingspecification cited above.

A heat or radiation exchanger including upper and lower manifoldstructures 414 and 416 as well as the interconnecting tubes or pipes 418exposes the feed stock, which is applied through input tube 420 andbrought out through tube 422, to the high temperatures and radiationpresent within the main reaction chamber 402.

At the center of the apparatus shown in FIG. 13 is a burner 424 to whcha lower inlet pipe 426 and an upper outlet pipe 428 are connected. Thiscentral burner unit may be of the type shown in FIG. 9 of the drawingsand as described hereinabove. The entire reaction chamber 402 shown inFIG. 13 is fully insulated and mounted as shown in FIG. 9, and equippedwith suitable automatic valving of the type described above inconnection with other embodiments of the invention.

In operation, steam is initially supplied to the reaction chamber 402through inlet line 430 when valve 432 is opened. Of course prior to thisinitial step, the reaction chamber 402 has been preheated to atemperature in the order of 1000° Kelvin, and the steam is suppliedunder high pressure. Hydrogen is then displaced by the action of thereactant, and the host/sensitizer materials included in tubes 412, asdescribed above. Hydrogen H₂ and hydrogen peroxide H₂ O₂ are drawn offthrough the upper manifold 404 and the connecting line 434 through valve436. During the hydrogen displacement phase of the cycle, additionaloxygen may be supplied through line 438 via valve 440. The additionaloxygen promotes the formation of hydrogen peroxide, which is, with thehydrogen, drawn off through line 434.

The overall cycle of reaction chamber 402 may be substantially asindicated by one of the two plots shown in FIG. 7. Accordingly with thesteam valve 432 and the valve 436 to the hydrogen storage tank bothclosed, the vacuum may be applied to the reaction chamber 402 so thatdisproportionation of the oxygen from the reactant takes place.

While the hydrogen displacement at high pressure and the oxygendisproportionation phase of the cycle at low pressure is occurring inthe main reaction chamber 402, the feed stock may be continuously passedthrogh the heat and radiation exchanger 414, 416, 418, at a suitablerate to maintain the desired high temperature and high level ofradiation of the feedstock. Incidentally the tubes 418 interconnectingthe upper chamber 414 and the lower chamber 416 may be made of mulliteincluding the host/sensitizer materials mentioned in the variousexamples given above. Similarly the manifolds 414 and 416 may be made ofsuch materials. Alternatively the elements 414, 416, and 418, may bemade of metal, such as stainless steel, to which suitable quantities ofhost/sensitizer materials have been added in order to give the desiredintimate irradiation action with regard to the feed stock.

Instead of using a single reaction chamber as shown in FIG. 13, a heatand irradiation exchange unit could be employed with a multiple reactionchamber apparatus such as that shown in FIG. 9. When used with amultiple reaction chamber arrangement such as that shown in FIG. 9, ofcourse the heat exchange elements must make sealing engagement with thewalls of the individual reaction chambers which will be at differentpressures during different portions of the individual staggered cyclesin the different reaction chambers.

It may be noted that, in accordance with disclosures in my priorco-pending patent application cited above, and teachings found elsewherein the present specification, the hydrogen and H₂ O₂ "tailings",obtained as a vacuum is being drawn on line 438, and such outputhydrogen and/or hydrogen peroxide from line 434 as may be desired, maybe applied through line 426 to the central burner 424. This may servethe purpose of supplying additional heat to the entire unit to permitmore rapid flow of feed stock through lines 420 and 422 without loss oftemperature in reaction chamber 402.

ENERGY BALANCE

In my prior co-pending patent application an "Energy Balance" sectionwas included. In the present specification, a portion of the prioranalysis will be set forth, and a more thorough energy analysisinvolving the new material in this application will be included.

In view of the fact that the apparatus of the present type and asdisclosed in my prior application are exothermic on a net basis and alsoproduces hydrogen or hydrogen peroxide which can be burned, there havebeen some suggestions that certain so-called Laws of Thermodynamics arebeing violated. This is of course not the case, as will be developed bythe Energy Balance analysis set forth below.

From an overall standpoint, the present system may be viewed asproviding an energy balance and not violating any "Laws ofThermodynamics" as a result of the low energy content gaseous productswhich are released in the course of the process. These low energygaseous products may include HO and HO₂, which are less well knowngaseous products. When these gaseous products are released into theatmosphere, it is believed that they absorb high frequency radiations,and eventually change state to become hydrogen gas, oxygen gas, watervapor, atomic hydrogen and atomic oxygen. In one sense, therefore, thepresent systems may be considered to utilize solar energy.

The stoichiometric reactions set forth below represent one of severalmodes of operation which may obtain in implementations of the presentinvention.

The foregoing equations may be analyzed from two different standpoints.Incidentally, it may be noted that the "2HO" designated (4) in the upperequation is actually evolved in the disproportionation phase. Inaddition, a portion of the hydrogen gas H₂ from (6) in the upperequation is an input in the lower equation which combines with thedisproportionated oxygen to form HO. Also, of course, the incidentphotons are applied in the atmosphere, and not in the apparatus per se.It should also be noted that the O₂ input designated (2) is essentiallyoptional and may involve the venturi unit 212 or inlet 217, of FIG. 6,whereby additional O₂ is supplied to generate H₂ O₂, as noted above.##STR1##

Now, the upper equation will be analyzed from a potential energystandpoint:

    ______________________________________                                        POTENTIAL ENERGY IN:                                                                       K. Cal                                                           ______________________________________                                        (1)     2 H.sub.2 O                                                                              141.2                                                      (2)     O.sub.2 + H.sub.2                                                                        43.2       = 421.543 K. Cal.                               (3)     h v        237.143                                                    ______________________________________                                    

    ______________________________________                                        POTENTIAL ENERGY OUT:                                                                   K. Cal                                                              ______________________________________                                        (4)  2HO        43.2                                                          (5)  H+O+O+H    223.96                                                                                  = 330.639 K. Cal. (H.sub.2 Out)                     (6)  H.sub.2, or                                                                              63.479   or                                                   (7)  H.sub.2 O.sub.2                                                                          114.262  381.422 K. Cal (H.sub.2 O.sub.2                      ______________________________________                                                                 Out)                                                  Efficiency (H.sub.2 Out) = 0.78                                               Efficiency (H.sub.2 O.sub.2 Out) = 0.90                                  

Actually, there is often a combination of H₂ and H₂ O resulting in anintermediate efficiency.

Now, from a Gibbs Free Energy (G) Analysis standpoint involving Enthalpy(Heat, H), Entropy (S), and temperature T, the following analysisobtains:

In the following analyses, the enthalpies and entropies of the startingreactants are subtracted from the enthalpies and entropies,respectively, associated with products. The letters "in" have beenassociated with the initial values relating to the starting products.

    ______________________________________                                        Oxygen Sequestering Reaction                                                  (Upper Equation designated "Stoichiometric Reaction")                         ΔH°.sub.form : 2(-70.6) (in) 2(-228.6) (in)                                               -43.26.7)                                                                     -43.2   -33.96                                       S°.sub.form : 2(+45.11) (in) 2(+26.4) (in) 4(+12.7)                                             +43.89                                                                        +43.89  +56.01                                       ΔH°.sub.react : -627.16-(-598.4) = -28.76 Kcal/Mol-Egn           ΔS°.sub.react : +194.59-(+143.02) = +51.57 Cal/Mol-Egn           × Deg.                                                                   ##STR2##                                                                     ΔG: ΔH - TΔS = -28.76-(+51.57)                              ΔG: = -80.33 Kcal/Mol-Egn                                               Reverse Reaction                                                              ΔH°.sub.form : 4(-126.7) (in) 2(-228.6)                                                   -43.2                                                S°.sub.form : 4(+12.7) (in) 2(+26.4)                                                            +43.89                                               ΔH°.sub.react : -500.4-(-506.8) = +6.40 Kcal/Mol-Egn             ΔS°.sub.react : +96.69-(+50.8) = +45.89 Cal/Mol-Egn ×      Deg.                                                                          TΔ S: 1000.sub.degrees × (+45.89) = +45.89 Kcal/Mol-Egn           ΔG: ΔH - TΔS = +6.40-(+45.89)                               ΔG = -39.49 Kcal/Mol-Egn                                                Complete Cycle                                                                ○ΔH = -28.76 + (+6.40) = -22.36 Kcal/Mol-Egn                     ○ΔS = +51.57 + (+45.89) = +97.46 Kcal/Mol-Egn                    ______________________________________                                    

From the foregoing analysis, it may be noted that the heat or enthalpyfor the hydrogen generation portion of the cycle is equal to -28.76 KCal/Mol-Eqn, which means that the reaction is exothermic. For the"Reverse Reaction" or the oxygen disproportionation part of the cycle,the heat or enthalpy figure is +6.40 K. Cal/Mol-Eqn. This means that thedisproportionation part of the cycle is endothermic, but that the heatrequired is much less than that generated in the other portion of thecycle. With thoroughly insulated equipment the heat generated during theexothermic portion of the cycle, in the same or other adjacent reactionchambers, is more than sufficient to provide the heat needed during thedisproportionation part of the cycle. It may also be noted that thepositive entropy value for the "Reverse Reaction", or thedisproportionation cycle, indicates that this reaction will go forwardspontaneously.

ENERGY BALANCE--SECOND MODE

Another pair of (1) Displacement of Hydrogen and (2) Disproportionationreactions appears below, together with a classical Gibbs Free EnergyAnalysis. Also included are the text citations for the entropy andenthalpy values used in the analysis. The following mode emphasizes theproduction of hydrogen peroxide, H₂ O₂, and carries over its use in thedisproportionation part of the cycle. It may also be noted that thefirst mode and second mode presentations are not precisely comparable asH₂ O.sub.(e) is assumed as an input for the first mode, and H₂ O.sub.(g)is assumed as an input for the second mode as set forth below. Asindicated by the negative value of the enthalpy for the two reactions ofthe second mode, it is also exothermic on an overall basis.

The equations for (1) hydrogen displacement and (2) oxygendisproportionation, are set forth below, together with their associatedEnthalpy (H), Entropy (S) and Gibbs Free Energy functions.

    __________________________________________________________________________    DISPLACING HYDROGEN                                                                   ##STR3##                                                              __________________________________________________________________________     ##STR4##                                                                             2(-59.24) 2(-228.39)                                                                           4(-123.63) 00       2(-33.96)                         ##STR5##                                                                             2(+55.59) 2(+40.13)                                                                            4(+19.46)  2(+39.70) 2(+49.00)                                                                    2(+70.94)                         ##STR6##                                                                             -562.44 - (-575.26) =                                                                          +12.82 Kcal/Mol - Eqn.                                ##STR7##                                                                             +397.12 - (+191.44) =                                                                          +205.68 Cal/Mol - Eqn. × Degrees                TΔS:                                                                           ##STR8##         +205.68 Kcal/Mol - Eqn.                              ΔG =                                                                           ΔH - TΔS = +12.82 - (+205.68) = -192.86                    ΔG =                                                                           -192.86 Kcal/Mol - Eqn.                                                __________________________________________________________________________    OXYGEN                                                                        DISPROPORTIONATION                                                                                                   ##STR9##                               __________________________________________________________________________     ##STR10##                                                                            4(-123.63)       2(-228.39)    -59.24  00                              ##STR11##                                                                            4(+19.46)        2(+40.13)     +55.59 +55.3 +42.83                     ##STR12##                                                                            -516.02 - (-494.52) = -21.50                                                                   Kcal/Mol - Eqn.                                       ##STR13##                                                                            +233.98 - (+77.84) =  +156.14                                                                  Cal/Mol - Eqn. × Degrees                        TΔS:                                                                           ##STR14##         Kcal/Mol/Eqn.                                       ΔG =                                                                           ΔH - TΔS = -21.50 - (+156.14) = -177.64 Kcal/Mol -         __________________________________________________________________________           Eqn.                                                                     ○ΔH  = +12.82 + (-21.50) = -8.68 Kcal/MolEqn.                   ○ΔS  = +205.68 + (156.14) = + 361.82 Kcal/MolEqn.           

The values for Enthalpy (H) and Entrophy (S) used in the foregoinganalyses are all taken from published texts as follows:

1.

MnO₂ Enthalpy (H) 900° K.=123.63

MnO₂ Entropy (S) 900° K.=19.46

2.

Mn₂ O₃ Enthalpy (H) 1000° K.=-228.39

Mn₂ O₃ Entropy (S) 1000° K.=40.13

Selected values of Chemical Thermodynamic Properties, by F. D. Rossiniet al, and U. S. Government National Bureau of Standards Accession No.6500390, N.B.S. Circular No. 500, dated Feb. 1952, pages 122 (MnO₂) and123 (Mn₂ O₃)

3. H₂ Entropy (S) 1000° K.=39.70

Thermodynamic Properties of the Elements Published November 1956,American Chemical Society, 1155 Sixteenth Street, N.W., Washington 6, D.C.

4. H₂ Enthalpy (H) 1000° K.=0 (By Definition)

5. O₂ Enthalpy (H) 1000° K.=0 (By Definition)

6. O₂ Entropy (S) 1000° K.=49.0

7.

H₂ O Enthalpy (H) 1000° K.=59.24

H₂ O Entropy (S) 1000° K.=55.59

"Thermodynamic Properties of Minerals and Related Substances . . ."--Geological Survey Bulletin 1259 Washington, D. C., U.S. Dept. of theInterior, 1968, p. 114.

8. OH Enthalpy (H) 1000° K.=9.13

9. H₂ O₂ Enthalpy (H) 1000° K.=-33.46

10. OH Entropy (S) 1000° K.=52.49

11. H₂ O₂ Entropy (S) 1000° K.=70.94

12. H₂ O Entropy (S) 1000° K.=55.59

TRC Tables, Selected Values of Properties of Chemical Compounds,Thermodynamics Research Center, Texas A&M University; Table 2 I T foritems 9-12 above; Table 2 I W for items 7 and 8 above.

From the negative value of -8Kcal/Mol-Eqn. of the enthalpy (heat) of theentire reaction, including both displacing hydrogen from water vapor anddisproportionating oxygen from the reactant, it is clear that theprocess is exothermic, in addition to generating hydrogen and/orhydrogen peroxide. And this surprising result, in one or the other or acombination of the modes described in the foregoing equations has beenconfirmed by the operation of prototypes using manganese oxide as thereactant.

Set forth below is a further analysis involving the photon dissociationof H₂ O, and an examination of the energy "borrowed from nature" and"returned to nature", or to the environment. In connection with thefollowing analyses, it may be noted that the energy for photondissociation of the H₂ O is obtained from the heat reservoir of hotreactant which is of course maintained at an elevated temperature by thenet exothermic nature of the hydrogen displacement and oxygendisproportionation cycle. When mention is made of the combustion of H₂O₂ in the following analysis, this combustion is in the course ofperforming useful work such as driving an engine, or the like, apartfrom the reaction chamber as described herein.

PHOTON DISSOCIATION OF H₂ O.sub.(g)

A. Average number of <(0.008)> particulates in 539.0 Cu. in. reactionchamber.

    =1.130859375×10.sup.9

B. Assuming radiated energy frequency averages <F>=3.64×10¹⁴ (second)

    ∴(1.130859375×10.sup.9)×(3.64×10.sup.14)

Photons=4.116.328.125×10²³ (second)

C. Assuming a continuum of 15 seconds

    15.0×(4.116328125×10.sup.23)

Photons in 15.0 Seconds=6.174492188×10²⁴

D. Since there are 6.02×10²³ photons in 1. mole (of photons) ##EQU4##Energy (15 sec.)=10.256632 moles photons

E. Converting to Kilocalories

    10.256632×26.48

Energy=271.60 Kilocalories (average)

F. Energy Required to Dissociate (1) Mole H₂ O.sub.(g)

    1 Mole=59.24 Kcal ##EQU5## G.

    ______________________________________                                        (1)   Dissociation by Reactant                                                                           2.00 Moles H.sub.2 O.sub.(g)                       (2)   Dissociation by Radiant Energy                                                                     4.58 Moles H.sub.2 O.sub.(g)                             Total                6.58 Moles H.sub.2 O.sub. (g)                      ______________________________________                                    

H. 6.58 Moles H₂ O.sub.(g) ≡5.22 cu. ft. H₂ O₂(g)

I.

1. cu. ft. H₂ O₂(g) =318 BTU

5.22 (cu. ft.)×318 (BTU)=1660.00 BTU

15.0 seconds=1.660.00 (BTU)=418.49 Kcal (Potential)

J. Energy Required to Operate Unit for 15.0 Seconds

    __________________________________________________________________________    (1) Dissociating 6.58 Moles Liquid Water at 70.6 Kcal/Mole                                                   = 389.8                                        (2) Sensible Heat Lost in Gases and Cooling Water                                                            = 22.4                                         (3) Radiated Heat Losses (all surfaces)                                                                      = 5.29                                         (4) Vacuum PUmp (1.0 H.P.)     = 0.27                                         (5) Water Pressure Pump (1.0 H.P.)                                                                           = 0.27                                         (6) Cooling Fan (Electronic Controls) (0.3 H.P.)                                                             = 0.10                                         (7) Cam-Motor and DC Controls (0.3 H.P.)                                                                     = 0.10                                         (8) Digital Readouts Power (0.1 H.P.)                                                                        = 0.03                                         (9) Compressed Air (0.5 H.P.)  = 0.14                                         (10) Compressed Hydrogen (0.5 H.P.)                                                                          = 0.14                                         TOTAL                            418.5                                        __________________________________________________________________________

K. Energy Balance=Output Minus Input

    418.5-418.5=0

    ______________________________________                                        BORROWED FROM NATURE                                                          (during 15.0 sec. period)                                                     A. Energy                  Kcal                                               ______________________________________                                        1. 658 Moles H.sub.2 O.sub.(1) × 70.6 Kcal/Mol                                                  =      389.8                                          2. Peripheral Equipment (15.0 sec.)                                                                          28.69                                          (Kcal) TOTAL            =      418.5                                          ______________________________________                                    

    ______________________________________                                        RETURNED TO NATURE                                                            A.    Potential Energy                                                        B.    Combustion of 5.22 cu. ft., H.sub.2 O.sub.2 × 318 BTU/cu.ft.               = 1660.00 BTU                                                                 = 418.5 Kilocalories -                                               Required Energy (from J) 418.5 Kcal                                           Energy from Combustion, 418.5 Kcal = 0                                        ______________________________________                                    

In closing, reference is again made to my copending patent applicationSer. No 768,808, filed Feb. 15, 1977, in which more detail is presentedrelative to the temperatures, pressures, and other reactions which maybe used. As noted in the prior specification, the temperature ofoperation should be above the dissociation temperature for oxygen forthe reactant being employed at atmospheric pressure. Advantageous highspeed results have been achieved with the reactant in the pyroplasticstate of incipient fusion. Concerning pressures, the pressure duringdissociation should be at least as low as atmospheric pressure, andpreferably a vacuum should be applied to reduce the pressure to afraction of atmospheric. The vacuum may be applied to draw the tailingsthrough the burner to extract additional heat from the tailings. Duringthe hydrogen displacement portion of the cycle the pressure should bewell above atmospheric to facilitate sequestering of the oxygen by thereactant. Successful results may be achieved with reactants such as MnOwith gauge pressures of about 100 to 130 or 150 and up to 500 pounds persquare inch. Even higher pressures may be employed. Concerning theactive reactant, as mentioned in my prior copending specification, itpreferably includes at least one metal having a plurality of valencestates. It should also have an oxide which will, when subjected to watervapor at elevated temperature and/or pressure, and preferably both,combine with the oxygen and displace the hydrogen in gaseous formexothermically. The reactant also preferably has the property ofdisproportionation or dissociation to release the combined oxygen whenthe temperature is raised or preferably when the pressure is reduced,and when the evolved oxygen is separated from the reactant.Advantageously, the heat required in the disproportionation part of thecycle is significantly less than that generated in the exothermicportion of the cycle when the reactant combines with the oxygen in thesteam and releases hydrogen, so the entire cycle is exothermic. Also,the reactant should be susceptible of remaining in the pyroplastic stateof incipient fusion during the change in state from one oxidation levelto another, and back again, under the described conditions.

Some of the metals and oxides thereof which fulfill the foregoingrequirements include (1) antimony, (2) cesium, (3) barium, (4) iron, (5)manganese, (6) chromium, (7) iridium, (8) nickel, and (9) thallium.Other metals which have multiple valence states are known, but most ofthese have practical problems which preclude their use. Thus, forexample, mercury has too low a melting point, and its oxides areunstable. In the case of other metals having multiple valence states,their oxides may be poisonous, they may be caustic or are not availablein practical or commercially available quantities. Other metals havingmultiple valence states have oxides which will not readilydisproportionate. Combinations of reactants satisfying the requirementsindicated above may be employed in the form of alloys, eutetics, andwith other materials to obtain desired temperature and mechanicalproperties.

FIGS. 14 and 15 are particularly useful in analyzing the apparatus ofthe present invention from a radiation standpoint. FIG. 14 showsspectral radiant emittance, or power in watts radiated at variouswavelengths from a "black body" having a temperature of 1000° Kelvin,while FIG. 15 is a similar plot showing photon emission, or the numberof photons emitted at various wavelengths. The FIG. 14 plot drops offmore rapidly than that of FIG. 15 because shorter wavelength photons aremore energetic and have higher power. In accordance with knownprinciples, the energy is directly proportional to the frequency andinversely proportional to the wavelength. It may also be noted that, inthe plots of FIGS. 14 and 15 the visible range is from about 0.4 to 0.7microns. Accordingly for the temperature of 1000° Kelvin (about 727°Centigrade and about 1341° Fahrenheit), which is plotted in FIGS. 14 and15, the radiation peaks in the spectrum at wavelengths somewhat longerand at frequencies slightly lower than the visible band.

FIGS. 16, 17, and 18 show a system for applying radiant energy to afeedstock. In FIG. 17 the feedstock is applied to reaction chamber 302by inlet tube 304 which is connected to manifold 306. Manifold 306 issupported by insulating ceramic material 308 which may either be in theform of a ring or a series of supporting blocks.

The reaction chamber has an outer cylindrical stainless steel wall 310secured to upper and lower stainless steel end plates 312 and 314. Thechamber 302 is provided with a cylindrical ceramic liner 316 and upperand lower inner ceramic end plates 318 and 320. Suitable insulation 322such as ceramic foam and an outer casing 324 are also provided.

A series of coated wires 326 extend for most of the length of thechamber 302 between upper and lower electrically conducting supportmembers 328 and 330. As shown in FIG. 16, the wires 326 are made up ofan inner wire 332 of conducting or resistive material and an outercoating 334 of ceramic material of radiation emitting material of one ormore of the types previously described.

The upper and lower wire supporting members 328 and 330 may be heldapart by the elongated ceramic member, and the metal rod 338 whichextends into the lower hollow end of ceramic member 336. The coatedwires 326 are heated up by the application of electricity to power inputconductors 340 and 342 to a temperature in the order of 1000° Kelvin.This causes a certain amount of thermal expansion in the wires, and byusing a suitable metal rod 338 which has a slightly higher coefficientof thermal expansion, the wires 326 may be maintained in operativepositions relative to each other.

In the case of a process involving steam as the feedstock and where itis desired to have hydrogen gas and H₂ O₂ as the output product, air maybe supplied either through input tube or pipe 304 and/or throughseparate input 344 to the apertured ring shaped manifold 346 which isheld in position by supports 348. Output product is drawn off throughpipe 350.

In practice, and as indicated in the block diagram of FIG. 18, air maybe supplied to the reaction chamber 302 either through input 304 alongwith the input feedstock such as steam, or through input 344 at theupper zone of the reaction chamber. When the air is supplied throughinput 344, toward the upper end of 302, it combines with thepreviously-formed hydrogen, resulting from dissociation of the watervapor, to form H₂ O₂.

Other blocks shown in FIG. 18 include a source of electrical power 354,a supply of liquid water at 356, a steam formation unit 358, and astorage container 360 for fuel gas such as gaseous hydrogen H₂ andhydrogen peroxide H₂ O₂. The supply line for water is indicated at 362,and that for air at line 364.

As indicated by line 366, a portion of the fuel gas which is formed maybe fed back to the steam formation unit 358 to increase the temperatureof the water vapor being supplied to reaction chamber 302. After theunit is in operation for a short period of time, the steam is suppliedto the reaction chamber 302 at a temperature well above the intendedoperating temperature of reaction chamber 302 so that little or noelectricity need be supplied from the source 354. Thus, for example,with steam being supplied at between 1100° and 1200° Kelvin, thetemperature of 1000° Kelvin desired within the reaction chamber 302 maybe sustained with the supply of very little or no electricity over line368.

With reference to FIG. 20, the coated wires 326 are shown supported by ascreen 370 which may be made of any suitable high temperature resistantconducting material. The wires 326 are woven in and out of the surfaceof the screen 370 to form the array as shown in FIG. 17. It may be notedthat the frame or support members 328 and 330 of FIG. 17 are shown asbeing formed of two parts. These two parts are open frame members whichclamp the screen 370 as shown in FIG. 20 and support it. If desired orif the conductivity of the particular coating employed in the system isrelatively low, the coated wires 326 may be scraped bare and weldedcontacts made at points such as those indicated at 372 in FIG. 20 tomake better conductive engagement with the screen 370 by whichelectricity is initially supplied to these wires. It is also noted that,instead of using the screen as shown in FIG. 20, the supportingstructures 328 or 330 may be simple perforated plates with the coatedwires 326 threaded through them.

Now, considering one specific example, the wires 326 of FIG. 17 may becoated with the host and sensitizer materials set forth in examples Nos.1 and 2 of the 15 examples set forth hereinabove in the presentspecification.

More specifically, before going into the example in detail, it may benoted that various units are used in the present specification inreference to the wavelength of the radiations which are employed. Forreference purposes and for ease in converting various units, it may benoted that the visible range extends from about 4000 Angstrom units to7000 Angstrom units, with an Angstrom unit being equal to 10⁻⁸centimeters. Expressed in microns this visible range corresponds towavelengths from 0.4 to 0.7 microns, with a micron being equal to 10⁻⁴centimeters. Similarly, when millimicrons are employed to measurewavelength, they correspond to 10⁻⁷ centimeters, and the visiblespectrum range is from 400 to 700 millimicrons.

It may also be noted, in converting frequency to wavelength and viceversa that the frequency of light is equal to 3 times 10¹⁰ cms. per sec.and that the product of frequency and wavelength is equal to thevelocity of light. Accordingly, using this simple expression that theproduct of the frequency times the wavelength is equal to the velocityof light, easy conversion may be made from frequency to wavelength, andvice versa. For convenience, reference is also made to Table I whichindicates the location of the visible light band relative to theinfrared and ultraviolet frequency bands, in addition to the remainderof the electromagnetic radiation spectrum.

                                      TABLE I                                     __________________________________________________________________________    TABLE 1-2 The Wavelength Frequency, and Energy of Typical Electromagnetic     Radiation                                                                      Approximate                                                                            Typical  Frequency,                                                                              Wave Number,                                                                           Energy,                                 Description                                                                            Wavelength, A                                                                           cycles/sec                                                                                cm.sup.-1                                                                           kcal/cinstein                            __________________________________________________________________________    Radio wave                                                                             1.00 + 10.sup. 13 (1000 m)                                                              3.00 × 10.sup. 5 (300 kc)                                                         1.00 × 10.sup.-5                                                                0.0000000286                             Short-wave radio                                                                       1.00 × 10.sup. 11 (10 m)                                                          3.00 × 10.sup. 7 (30 Mc)                                                          1.00 × 10.sup.-2                                                                0.00000286                                wave                                                                         Microwave                                                                              1.00 × 10.sup. 8 (1 cm)                                                           3.00 × 10.sup.10                                                                  1.00    0.00286                                  Far infrared                                                                           1.00 × 10.sup. 5 (10 μ)                                                        3.00 × 10.sup.13                                                                  1.00 × 10.sup.3                                                                 2.86                                     Near infrared                                                                          1.00 × 10.sup. 4 (1 μ)                                                         3.00 × 10.sup.14                                                                  1.00 × 10.sup.4                                                                 28.6                                     Visible light                                                                  Red     7.00 × 10.sup. 3 (700 mμ)                                                      4.28 × 10.sup.14                                                                  1.43 × 10.sup.4                                                                 40.8                                      Orange  6.20 × 10.sup.3                                                                   4.84 × 10.sup.14                                                                  1.61 × 10.sup.4                                                                 46.1                                      Yellow  5.80 ×  10.sup.3                                                                  5.17 × 10.sup.14                                                                  1.72 × 10.sup.4                                                                 49.3                                      Green   5.30 × 10.sup.3                                                                   5.66 × 10.sup.14                                                                  1.89 × 10.sup.4                                                                 53.9                                      Blue    4.70 × 10.sup.3                                                                   6.38 × 10.sup.14                                                                  2.13 × 10.sup.4                                                                 60.8 Photo- chemistry region              Violet  4.20 × 10.sup.3                                                                   7.14 × 10.sup.14                                                                  2.38 × 10.sup.4                                                                 68.1                                     Near ultraviolet                                                                       3.00 × 10.sup.3                                                                   1.00 × 10.sup.15                                                                  3.33 × 10.sup.1                                                                 953                                      Far ultraviolet                                                                        2.00 × 10.sup.3                                                                   1.50 × 10.sup.15                                                                  5.00 × 10.sup.4                                                                 142.9                                    Schumann ultra-                                                                        1.50 × 10.sup.3                                                                   2.00 × 10.sup.15                                                                  6.67 × 10.sup.4                                                                 190.6                                     violet                                                                       Long X-ray                                                                             3.00 × 10.sup.2                                                                   1.00 × 10.sup.16                                                                  3.33 × 10.sup.5                                                                 953.0                                    Short X-ray                                                                            1.00      3.00 × 10.sup.18                                                                  1.00 × 10.sup.5                                                                 285,910 chemistryRadiation region        Gamma ray                                                                              1.00 × 10.sup.-2                                                                  3.00 × 10.sup.20                                                                  1.00 × 10.sup.10                                                                28,591,000                               __________________________________________________________________________

With the foregoing background, reference is again made to examples Nos.1 and 2 of the 15 numbered examples set forth earlier in the presentspecification. It may be noted that the emission, for Example No. 1 wasapproximately 0.69 microns corresponding to a frequency of approximately4.34×10¹⁴ cycles per second. This corresponds to a red color in thevisible spectrum. Example No. 2 provides a yellow output light with awavelength of approximately 0.59 microns corresponding to a frequency ofapproximately 5.08 times 10¹⁴ cycles per second. Incidentally, anotheryellow line is produced by the materials of Example 12, with awavelength of 0.61 micron, corresponding roughly to 4.91 times 10¹⁴cycles per second.

Referring back to FIG. 17, one-half of the wires extending from support328 to support 330 are coated with material providing red outputradiation such as specified in Example No. 1 referred to above, andone-half of the wires are coated with material providing a yellow outputradiation. These wires are threaded through the supports 328 and 330 soas to be interspersed with one another so that the yellow and red outputradiation wires are not grouped together but are entirely interspersedwith one another.

When feedstock is supplied to the reaction chamber 302, the radiationwill be directed from the wires to the medium and the radiation ofdifferent frequencies will impinge upon the discontinuities provided bythe feedstock vapors and will beat with one another and will beconverted into sum and difference frequencies. More specifically,cnsidering examples Nos. 1 and 2, the frequency for the red radiation ofExample 1 was approximately 4.34 times 10¹⁴ cycles per secod, and thefrequency for Example No. 2 was approximately 5.084 times 10¹⁴ cyclesper second. One frequency which will be formed as these radiationsimpinge on the feedstock will be the sum frequency equal toapproximately 9.42 times 10¹⁴ cycles per second. This corresponds to awavelength of about 0.32 microns, in the near ultraviolet frequencyspectrum. Water vapor has a number of absorption peaks in the nearultraviolet frequency spectrum and these peaks are broadened by theelevated temperature present at 1000° Kelvin at which the reactionchamber 302 is operated. Accordingly, in addition to the dissociationaction produced by the direct radiation at the red and yellow frequencybands, the powerful ultraviolet radiations will have a strongdissociative effect on the water vapor being transmitted through thereaction chamber 302. Incidentally, the energetic nature of theradiations in the near ultraviolet may be noted from the far right-handcolumn in Table No. I in which the radiation in the near ultraviolet isshown to have an energy level in the order of double that in the red andyellow regions of the visible spectrum.

Attention is also directed to the plot of FIG. 21 showing the absorptioncharacteristic for hydrogen peroxide H₂ O₂ which is being formed in theradiation chamber 302. More specifically, it may be seen that theabsorption coefficient increases rapidly from the near ultraviolet rangeof 3000 Angstroms, or about 0.3 microns, to the far ultraviolet rangetoward the left of FIG. 21. Accordingly, with near ultraviolet radiationbeing employed in the chamber of FIG. 17 (reaction chamber 302) todissociate water vapor, it may be noted that the desired product gas H₂O₂ will be little affected and will be essentially transparent to thisnear ultraviolet radiation and will thus remain in its H₂ O₂ chemicalstate, after it is formed, without adverse effect from the nearultraviolet radiation.

FIG. 19 shows a alternative reaction chamber 376 which is divided intoan upper section 378 and a lower section 380. Dividing these twosections of the chamber is a perforated ceramic plate 382. In addition,two different sets of coated wires 384 in the upper section and 386 inthe lower section, are provided. These two sets of wires areelectrically interconnected by the links 388 which extend through theceramic plate 382 and join the lower support 390 for the upper set ofwires 384 to the upper support 392 for the lower set of wires 386. Apartfrom being divided into two chambers with two sets of different coatedwires in the upper and lower portions 378 and 380 of the reactionchamber 376, the chamber of FIG. 19 is generally similar inconfiguration to that of FIG. 17.

With regard to the nature of the coatings on the wires 384 and 386, theupper wires 384 are coated as described above in connection with FIG. 17to produce ultraviolet radiation.

The lower set of wires 386, however, are coated to provide strong outputradiation in the infrared radiation spectrum, as disclosed hereinabovein connection with examples A, B, and C. Accordingly, the arrangement ofFIG. 19 is organized to provide powerful radiation in portion 380 whichwill impinge vigorously on the feedstock and provide an initial verysubstantial dissociative effect on the water vapor. Then, in the upperportion 378 of the reaction chamber the dissociation of the water vaporis continued, but at a frequency in the near ultraviolet range which isclearly at a frequency spectrum with respect to the hydrogen peroxide,H₂ O₂, product gas which will not adversely affect or dissociate it. Thecombined effect of the two stage radiation chamber with differentradiation frequencies being employed in each of the two chambers, issuch as to maximize the production of the desired output gas.

Of course, in connection with FIGS. 16 through 21, two specific examplesof reaction chamber arrangements employing radiation to produce desiredproduct gases have been set forth. It is to be understood that throughthe examination of the spectral absorption characteristics of thefeedstocks and products, and by suitably providing radiation within thereaction chamber matched to the characteristics of the feedstock and theproduct, many other similar combinations may be developed by thoseskilled in the art.

It is also particularly to be noted that through the use of coatedwires, the amount of intial heat input required to raise the reactionchamber to operating temperature conditions, is greatly reduced.

For completeness, one set of dimensions for the wires 326, 384 and 386will now be given. The overall diameter of the coated wires may be0.00257 inch, and the diameter of the inner metal wire is 0.00157 inchwith the coating being about 0.0005 inch thick, adding aboutone-thousandth of an inch to the diameter. The inner metal wires may,for example, be made of tungsten or other metal having a relatively highmelting point and adequate strength at 1,000° Kelvin.

FIGS. 22 and 23 show an alternative arrangement for applying highfrequency radiation to feedstock supplied to a reaction chamber. In FIG.22 the reaction chamber per se is made up of two hemispheres 402 and 404which are secured together by bolts 406 which extend through the matingflanges 408 and 410 of the hemispheres 402 and 406. An outer sheet metalhousing 412 is provided to enclose the unit and to support the variousenclosed elements of the system. Thus, for example, the hemispheres 402and 404 are supported from brackets 414 secured to the housing 412.Between the reaction chamber 402, 404 and the housing 412 is suitableinsulation for 416 of the ceramic foam insulation type.

Feedstock is supplied to the reaction chamber 402, 404 through inputpipe 418, and product gases are withdrawn from the reaction chamberthrough pipe 420.

Input radiation is supplied to the reaction chamber 402, 404 through thewindow 422 which may, for example, be made of high temperature resistantquartz glass.

FIG. 23 is taken along line 23--23 of FIG. 22. Shown to advantage inFIG. 23 are the two lasers 424 and 426 which direct coherent radiationof different colors through the window 422 into the reaction chamber402, 404 which has a highly polished interior surface. One of the lasers424, 426 is a ruby laser with output radiation in the red spectralregion, while the other laser is an yttrium aluminum garnet, or Yaglaser with output radiation in the green frequency band. These lasersare directed at an acute angle through the window 422 so that theradiation of the two lasers beat to produce a higher frequency in theultraviolet spectrum, as discussed and developed hereinabove inconnection with the radiation from the wires of FIGS. 17 and 19.Accordingly, the feedstock supplied to the reaction chamber through thepipe 418 will be irradiated not only with the red and green direct laserillumination, but also by the beat frequencies which arise when the redand green radiation impinge on the discontinuities provided by thefeedstock materials supplied to the chamber.

It may also be noted that in all of the embodiments described herein,where additional oxygen is supplied, and hydrogen peroxide, or H₂ O₂, isformed, this reaction is exothermic and supplies heat to the reactionchanmber. This factor is useful in increasing the efficiency of theprocesses, and contributes to the self-sustaining nature of theprocesses, as discussed above.

On a general basis, the processes described herein provide a mechanismfor the transformation of low grade thermal radiation into specificcoupled modes of intense monochromatic radiation providing new higherfrequencies and shorter wavelengths with considerably increased power.

The energy change is accomplished through the creation of controlledspatial harmonics beating together while passing through mediadiscontinuities within a non-linear medium. The effect is much like aparametric amplifier which controls the disposition of theelectromagnetic energy conveyed by the waves. On a comprehensive basis,the transformation of the broad black body radiation into specificmonochromatic frequencies of high energy which are matched to theabsorption bands of the feedstock and to the transmission bands of theproduct, make for process efficiencies which are extremely high.

With regard to the operating temperatures and pressures for theapparatus of FIGS. 16 through 19, and that of FIGS. 22 and 23, thetemperatures and pressures are less critical than for the embodimentsdisclosed earlier in the present case. In general, in order to provideradiation in the desired spectral range the apparatus of FIGS. 16through 19 should be operated at a temperature in the order of 1000°Kelvin; however, other temperatures may be employed which produceadequate radiation at the desired frequencies, and a departure of 100°or 200° above or below 1000° K. would be operative, it is expected, withradiation drop off toward the lower end of this temperature range andpossible materials failure problems toward the upper end of the range.Concerning the embodiment of FIGS. 22 and 23, a lower temperature suchas 250° F., above the boiling point for water at the pressure which isemployed, would be adequate.

Concerning pressures, somewhat lower pressures are adequate, as comparedwith the embodiments involving the use of metallic oxides, and no changein pressure is needed. For the embodiments of FIGS. 22 and 23, a gaugepressure of 3 or 4 pounds would be adequate, although higher pressuresof up to several hundred pounds, for example, could be employed wherehigher fuel gas reservoir pressures are desired. Similar pressureconsiderations are applicable to the apparatus of FIGS. 16 through 20.

The apparatus of FIGS. 1 through 23, described hereinabove, were alsodescribed in the co-pending patent applications of which the presentpatent application is a continuation-in-part. New FIGS. 24 through 32will now be described.

FIG. 24 represents an alternative form of reaction chamber which may beemployed in a system substantially conforming to FIG. 18 of the presentdrawings. More particularly, the reaction chamber 502 of FIG. 24 couldbe employed as the reaction chamber 302 of FIG. 18.

Referring more particularly to FIG. 24, it includes an outer cylindricalshell 504 which may, for example, have a stainless steel interiorsurface, and contains a substantial number of closely spaced mercuryvapor lamps 506 having quartz envelopes. The mercury vapor dischargetubes 506 may, for example, be cold cathode tubes and have electricalterminals 508 at one end of the chamber, and 510, at the lower end ofthe reaction chamber 502. The mercury vapor discharge tubes 506 may besupported by the upper and lower aluminum plates 512 and 514.

Apertured transverse plates 516, 518 and 520 extend transversely acrossthe reaction chamber 502, and plate 518 may serve much the same functionas the transverse baffle 382 in FIG. 19. Feedstock is applied toreaction chamber 502 through inlet 522 at the bottom of the reactionchamber, and the output products from reaction chamber 502 are carriedoff through tube 524. The space below baffle 516 serves as an inputmanifold, while that above baffle 520 serves as an output manifold. Inaccordance with the reaction which is to be undertaken, the radiation inthe input portion of the reaction chamber 502, between baffle plates 516and 518, may be of a somewhat different frequency of radiation, thanthat in the output irradiation portion of the reaction chamber 502between baffle plates 518 and 520. The design factors going into theirradiation and to specific frequencies in the input and output sectionsof the reaction chamber were discussed hereinabove in connection withthe embodiment of FIG. 19. Similar considerations, of course, applyhere.

The physical mounting arrangements and electrical connections for eachmercury vapor tube may be provided as indicated in FIG. 25. Moreparticularly, as shown in FIG. 25, the mercury arc lamps 506 areprovided with conducting terminals 508 which are silver soldered to theexisting pins extending from the ends of commercially available mercuryarc lamps. A thick silicone rubber sheet 526 is provided to support,cushion and locate the ends of the mercury arc lamps 506. In addition,the silicone rubber heavy wall tubes 528 enclose the electricalterminals 508 and insulate them from the aluminum conducting end plate512. The sheet 526 and tubes 528 may be either integral or separate,with the tubes ending even with the lower surface of plate 512.

Helically wrapped around the outer cylindrical surface of the mercuryarc tubes 506 are filaments 532 which are formed of laser-type material.The laser-type material included in the filaments 532 may be of the hostand sensitizer type as discussed hereinabove, or they may be of rubylaser-type material, if desired.

The mercury arc tubes 506 extend through clearance holes in the plates516, 518 and 520. As indicated in FIG. 26, the plate 520 is providedwith holes 534 which are of slightly larger diameter than the outerdiameter of the tubes 506. If desired, the tubes may be firmly supportedas indicated in FIG. 25 at both ends of the reaction chamber and merelypass freely through the plates such as plate 520 of FIG. 26.Alternatively, each of the apertures in plate 520 may be grooved toreceive a lamp retaining spring which will provide additional supportand location to each of the mercury vapor lamps. These lamp retainingsprings 536 are shown schematically in FIG. 26.

The filaments 532 and 532' of FIGS. 27 and 28, respectively, may includea central metal filament 538 which may be of resistive material asdisclosed hereinabove in connection with FIG. 16 of the drawings, or thefilaments may be made up entirely of laser-type material, as indicatedin FIG. 28. The central metal filaments 538 may be employed to ohmicallyheat the filaments to an elevated temperature to produce the desiredoutput radiation as discussed above in connection with the embodimentsof FIGS. 17 and 19, for example. Under these operating conditions,electricity would be applied both to the individual filaments to heatthem to the proper temperature, and also across the terminals 508 and510 of the mercury gas discharge tubes to appropriately energize them.

The laser-type materials for use in the coating 540 of FIG. 27 or as theentire filament in FIG. 28 may be of any of the host-sensitizer types asdiscussed hereinabove in connection with other embodiments of theinvention. Alternatively, other known laser materials such as suitablydoped aluminum oxide, used in the ruby laser, may be employed. Otherknown laser materials may also be used.

To enhance laser action, the filaments 532 or 532' of FIGS. 27 and 28,respectively, may be provided with one or more semi-transparent, orpartially reflective layers 544 and 546 (see FIG. 27), or 548constituting an outer peripheral partially transparent metallic coatingon the outer surface of filament 532', in FIG. 28. The semi-transparentsurfaces 544, 546, and 548 may be made by depositing a thin layer ofchromium or other good reflecting material on the filament 532 or 532'as they are being formed. The distance between substantiallyperpendicular surface areas of the semi-transparent layers 544 and 546,for example, along the line segment 550, should be an integral multipleof half wavelengths, in order to maximize lasing effect and to productessentially coherent output radiation. Similarly, the diametral distance552 in FIG. 28 should be an integral number of half wavelengths at thedesired output radiation frequency.

Concerning the radiation within the reaction chamber, it is a functionof the output radiation both of the mercury arc lamps 506, and also theradiation produced by the filaments 532 and/or 532'. With mediadiscontinuities within the reaction chamber caused by the presence offeedstock within the reaction chamber, the different frequencies whichare generated will "beat" with one another and produce sum anddifference frequencies. Thus, for example, if ruby laser-type materialis employed as the laser-type material as indicated by the referencenumerals 540 and 542 in FIGS. 27 and 28, respectively, the radiationwavelength is approximately 7.0×10³ Angstrom units. The output radiationfrom the mercury arc lamps includes a prominent spectral line at2.537×10³ Angstrom units, and a very broad emissions band which peaks atabout 3.0×10⁴ Angstrom units. When these radiations impinge on the mediadiscontinuities provided by water vapor feedstock, for example, theresultant sum frequency has a wavelength of approximately 1.752×10³Angstrom units, in the ultraviolet frequency spectrum. This highfrequency ultraviolet radiation is within the U. V. absorption band ofwater vapor as shown in FIG. 29 of the drawings. Accordingly, by way ofexample, this combination of frequencies may usefully be employed in theinput section of the chamber of FIG. 24 between the baffles 516 and 518.This is particularly useful in this area in view of the high energycontent of the 1.7×10³ Angstrom unit ultraviolet radiation, and the lowconcentration of hydrogen peroxide in the input section of the reactionchamber. As noted in FIG. 21, H₂ O₂ has a relatively high absorptioncoefficient for 1.7×10³ Angstrom radiation, and it is preferred that farultraviolet radiation of this type not be used in the output section ofthe reaction chamber 502, between baffle plates 518 and 520, where highconcentrations of H₂ O₂ are present, for most efficient use of theradiated energy. On the other hand, in this output region, it would bepreferable to have irradiation of the water vapor at lower frequenciesand longer wavelengths, to couple to selected water vapor absorptionbands that are present at longer wavelengths as shown in FIG. 10 of thedrawings, thereby avoiding absorption of the radiation by hydrogenperoxide. Suitable materials for producing such radiation are disclosedhereinabove in Examples (a) through (e) in the section of thisspecification entitled "Host/Sensitizers for Water Vapor Feedstock".Similarly, other design controlled radiation systems may be developedfor both the input sections and the output sections of the reactionchamber 502 to smoothly facilitate the desired dissociation andrecombination chemical reactions.

FIGS. 30, 31, and 32 of the drawings show an important embodiment of theinvention in which spheres are employed in proximity to the outersurface of the gas discharge tubes, instead of the filaments shownhereinabove. Specifically, as shown in FIG. 30, the outer surface of allof the quartz mercury vapor tubes 506 are provided with a large numberof spheres 556. These spheres may be formed of any of the laser typematerials, or the host-sensitizer materials discussed hereinabove, andthey are preferably coated with a semitransparent metallic coating tofacilitate the radiation of substantially coherent radiation. Withregard to dimensions, the quartz tubes 506 may be in the order of 3/4inch in diameter; the spheres 556 may be in the order of 0.002 to 0.004inches in diameter, and the semireflecting coatings are preferablyspaced apart along a diametral line by an integral number of halfwavelengths at the output radiation frequency of the laser typematerial. The spheres 556 may be secured in proximity to the outersurface of the tubes 506 in any desired manner, preferably by the use ofglass frit, fired when the spheres are firmly held against the quartzenvelope by a suitable high temperature wrapping. The spheres may occupyin the order of 50% of the area of the tube, or a greater or lesser areadepending on the scheduled relative radiation from the mercury vaporlamps and the laser spheres, which is desired for the reaction beingundertaken.

As more clearly shown in the diagram of FIG. 31, the reflective coatingextends over most of the outer surface of sphere 556 but stops at line558. With the reflective coating not present where sphere 556 engagesthe outer surface of gas discharge tube 506, the pumping radiation fromthe mercury gas discharge, indicated by rays 560, has easy access to thelaser material within sphere 556, by passing through the transparentglass frit 566.

In the diagram of FIG. 31, the pumping radiation 560 serves to raise theatoms in the laser-type material to the excited state; and the rays 562represent the coherent radiation characteristic of laser materials,which is generated as atoms drop from the excited state to lower energylevels triggered by arriving radiation from other transitions within thesphere. The reflecting coating on the outer surface of sphere 556 ispreferably in the order of 70% to 90% reflecting and only 30% to 10%transmissive in order to enhance the generation of harmonic radiation.Accordingly, the output radiation as indicated by the rays 564 may havea significant energy content which is at a frequency which is a multipleof the basic output frequency of the laser material in sphere 556.

For example, with the ruby laser having a fundamental radiationwavelength of just under 7,000 Angstrom units, the fourth harmonic wouldhave a wavelength of about 1,750 Angstrom units, in the far ultraviolet.

Incidentally, as shown in FIG. 31, the transparent glass frit 566 isshown securing the spheres 556 onto the quartz envelopes 506. Withsuitably transmissive material being selected for the frit 566, and withthe semi-reflective coating stopping at line 558, the mercury vaporradiation from within the discharge tubes readily passes into thespheres 556.

In the diagram of FIG. 32 the quartz envelope 506 separates the gasdischarge region 572 from the reaction chamber region 574. In the gasdischarge region 572, electrons 576 are shown moving at high velocitiesdownward, and the heavy ionized mercury molecules 578 are driftingupwardly. Collisions cause the radiation of energy from the mercuryvapor, and the complex atomic structure of mercury produces radiation ata large number of spectral lines. The resultant radiation is shownschematically at 582, 584, and 586.

Within the reaction chamber region 574 are shown water vapor molecules592, oxygen molecules 594 and hydrogen molecules 596, with the showingsbeing in the form of circles of progressively reduced size. It is alsointeresting to note that some of the radiation from the ionized mercuryvapor provides pumping energy to spheres 556, and some of the radiationpasses directly into the radiation chamber region 574.

CHAIN REACTIONS

The apparatus of the present invention are particularly well suited forthe implementation of chain reactions. This is particularly true of thereaction chambers shown in FIGS. 19 and 24, in which differentfrequencies of radiation may be applied to incoming feedstocks ascompared with feedstocks during the subsequent portion of the chainreactions.

In considering the mechanisms involved in photochemical kinetics, it isimportant to recognize that most complete photochemical reactions may bedivided into three somewhat overlapping stages: (1) The initial act ofabsorption of radiant energy, (2) the primary process, and (3) secondaryreactions.

Background texts relating to this subject matter include "Photochemistryof Gases", by William Albert Noyes, Jr. and Philip Albert Leighton,published in 1941 by Rheinhold Publishing Company; "Combustion, Flamesand Explosions of Gases", published by Academic Press, Inc., 1961, byLewis and Von Elbe; and "Photochemistry", by Calvert and Pitts,published by Wiley, in 1966.

One form of chain reaction which is diagramed below involves theabsorption by molecule A by radiation such as light, and itsdissociation into identical fragments. The secondary reactions involve achain which may be stopped at low pressures by the removal of thecarriers at the walls, and at high pressures by a homogeneousrecombination involving a third body or reactant. The overall reactionproduced by the chain is A+B→2C. Various examples are to be found among"halogenation" and "hydrogen-oxygen" reactions. The mechanism is asfollows:

    __________________________________________________________________________             PRIMARY:    (1)                                                                              A + hv→D.sub.1 + D.sub.1                                            (2)                                                                              D.sub.1 + B→C + D.sub.2                                 CHAIN:      (3)                                                                              D.sub.2 + A→C + D.sub.1                        CHAIN    LOW-PRESSURE                                                                              (4)                                                                              D.sub.1 + S→1/2A + . . .                       BREAKING                                                                               (SURFACES)  (5)                                                                              D.sub.2 + S→X + . . .                                               (6)                                                                              D.sub.1 + D.sub.1 + M→A + M                             HIGH-PRESSURE                                                                             (7)                                                                              D.sub.2 + D.sub.2 + M→Y + M                    __________________________________________________________________________

Concerning radiated energy effects, when a molecule or a polyatomic ionis irradiated by electromagnetic energy of a wavelength appropriate tocouple with the molecule or ion, this radiation may be absorbed, and theenergy of the molecule or polyatomic ion may be increased; the moleculeor ion may be excited rotationally, vibrationally, or electronically, orone or more of the covalent bonds that hold the molecule together may bebroken. This bond-breaking gives rise to the formation of atoms, orgroups of atoms, which have one "unpaired" electron each and are called"free radicals".

Accordingly, the absorption of radiated energy by a molecule may causeit to decompose into fragments or free radicals, which are extremelymore reactive than the original molecule. When this is the case, thesequence of reaction steps leading to the final products involves thesefree radicals (even though they may exist only temporarily in thereaction mechanism), rather than the original molecules of the reactant.

CHAIN REACTION EXAMPLE NO. 1

The first example of chain reactions which we will consider involves thereaction of hydrogen gas H₂ with Chlorine gas Cl₂ to form HCL gas. Whena Cl₂ molecule absorbs radiated energy it passes to a higher energy oran excited state, and if the energy of this excited state issufficiently high, the bond of the Cl₂ molecule may be broken to formtwo Cl atoms. In this connection it may be noted that in order todissociate a Cl₂ molecule into its two atoms, a relatively largequantity of energy, in the order of 58.16 kilocalories per mole of Cl₂gas must be supplied. The decomposition of Cl₂ molecules by absorptionof radiated energy is illustrated by the following equations, which alsoinvolve the presence of hydrogen gas:

    ______________________________________                                         (1)                                                                                   ##STR15##         (ΔH = +58.16)                                 (2)                                                                                   ##STR16##         (ΔH = +7.02)                                  (3)                                                                                   ##STR17##         (ΔH = -51.14)                                ______________________________________                                         ○ΔH +7.02 + (-51.14) = -44.12 KCAL                          

The chain reaction is eventually broken when a Cl atom collides withanother Cl atom, perhaps absorbed on the wall of the reaction chamber,to reform a Cl₂ molecule. The chain reaction may also be interruptedwhen a Cl atom reacts with some impurity present in the system to form aproduct which no longer contributes to maintaining the chain reaction.

CHAIN REACTION EXAMPLE NO. 2

This second chain reaction example involves the reaction of methane CH₄with Chlorine Cl₂ to form methyl chloride, CH₃ Cl, and hydrogen chlorideHCl.

The primary reaction is as follows: ##STR18##

The chain initiation step involves the absorption of radiated energy bythe Cl₂ molecule to break the bond as in the previous example: ##STR19##

Various chain propagation steps now follow. First, a Cl atom of highkinetic energy comes in contact with a CH₄ molecule, a carbon-hydrogenbond is broken, while a hydrogen-chlorine bond is formed. By losing an Hatom, the CH₄ molecule becomes a CH₃ radical: ##STR20##

Now, a methyl radical CH₃ comes in contact with a Cl₂ molecule; achlorine-chlorine bond is broken, while a carbon-chlorine bond isformed. The products are a methyl chloride molecule and a chlorine atom:##STR21##

The two chain propagation steps 2 and 3 are repeated many times beforethe chain reaction is broken by adverse reactions or one of severalchain terminating reactions of the type mentioned hereinabove.

The uniformity of radiation extending throughout the reaction chambersas disclosed in the present patent application is particularlyadvantageous in reactions such as the formation of methyl chloride CH₃Cl. This advantage arises particularly from the fact that thesubstitution of chlorine atoms can proceed further, forming the di-,tri-, and finally the tetra-chlorocompound, CH₂ Cl₂, CHCl₃, and CCl₄.

It is understood that an H atom of CH₃ Cl is more readily substituted,or replaced by a Cl atom than is an H atom of methane, CH₄. Also, an Hatom of CH₂ Cl₂ is more susceptible to further substitution by a Cl atomthan an H atom of CH₃ Cl₂, and similarly for CHCl₃. In the present case,the C--H bond becomes more readily susceptible to substitution by aCl--Cl bond as the number of Cl atoms already attached to the C atomincreases. In terms of energetics, the compound CH₃ Cl isthermodynamically stable with respect to a mixture of CH₄ and Cl₂, butthe di-, tri-, and tetra- substituted compounds, CH₂ and Cl₂, CHCl₃, andCCl₄, are even more stable, their stability increasing with the numberof Cl atoms in the molecule.

If a reaction chamber were irradiated unevenly, with certain localizedareas of very intense radiation, and others where there was littleirradiation, then the reaction would proceed to the (undesired) finalproduct CCl₄. However, in the present case, by using reaction chamberswhich are very uniformly flooded with radiation, the bulk of the methaneis only subject to a single substitution of the activated chlorine atomCl, and it occurs very soon after these highly activated chlorine atomsare formed by the impact of radiation on the chlorine gas Cl₂. Inaddition, a substantial excess of CH₄ is provided. Therefore, underthese conditions, CH₃ Cl is the principal product of the chlorination ofmethane, although the more substituted products may also be formed inmuch smaller yields. In accordance with the teachings of the presentinvention, and the apparatus disclosed therein, precise amounts ofenergy of the proper energy level are delivered evenly throughout thereaction chamber, with the photons bombarding the target molecules,atoms or fragments of molecules from all directions simultaneously. Inaddition, as mentioned above, large amounts of intense energy ofcontrolled wavelengths coupled to absorption bands of specific moleculesor atoms is provided. This eliminates the steric factor, which is anormally expected problem.

PHOTOCHEMISTRY OF WATER VAPOR

The absorption spectrum of water vapor in the ultraviolet region isshown in FIG. 29. As compared with FIG. 10, it may be noted that FIG. 29is directed to a band which starts just below 2,000 angstrom units. Thiswould correspond to 0.2 microns. As mentioned hereinabove, the visiblespectrum ranges from about 4,000 to about 7,000 angstroms, which isequal to 0.4 to 0.7 microns. Accordingly, the plot of FIG. 29 is in theultraviolet, well below the visible spectrum, and the plot of FIG. 10 isin the infrared, above the visible spectrum. In comparing FIGS. 10 and29 it may also be noted that in FIG. 29 peaks of absorption extendupwardly, whereas in FIG. 10 peaks of transmittance are plottedupwardly, and peaks for absorption extend down toward zero on thevertical scale.

There is considerable evidence that the photolysis of water at allwavelength regions leads to hydrogen and OH radicals. The followingprimary reactions are probably significant: ##STR22##

These reactions become possible energetically at wavelengths less than2,420 angstrom and are probably the major reactions in the longerwavelength absorption bands of ultraviolet radiation. At wavelengthsless than 1,356 A° units, another reaction leading directly to theobtaining of excited individual oxygen atoms, is understood topredominate.

As the dissociation/formation processes proceed in our examples, thecleavage or fragmenting of the H₂ O, O₂, or H₂ molecules yield H--OH,O--H, HO--OH, HO₂ --H, H--O₂, HO--O, H--H, and O--O products. Amongthese are very "hot" radicals, fragments, or atoms, because as describedearlier, the greater part of the surplus energy that is absorbed iscarried away by the latter fragments or atoms. Although in the case ofan oxygen or hydrogen molecule, where scission of either of thesemolecules results in an equivalent weight distribution, actually, eitheror both atoms may become hot atoms, especially under constantbombardment. Then, each single atom or fragment, or radical, is capableof initiating a chain and/or a branching chain reaction, by destroying anormal H₂ O, H₂, or O₂, and H₂ O₂ molecule.

CHAIN REACTION EXAMPLE NO. 3

In this and the next example, chain reactions involving water vapor andoxygen will be considered: ##STR23##

The foregoing chain reaction number 3 will now be analyzed from a Gibbsfree energy standpoint, with the numbers in the following analysiscorresponding to the equations set forth above. ##STR24##

CHAIN REACTION EXAMPLE NO. 4

This example like the previous example, involved the reaction of watervapor and oxygen when high intensity and high frequency radiant energyis applied to it.

    __________________________________________________________________________    PRIMARY REACTION                                                               ##STR25##                                                                     ##STR26##                                                                    ○H°AVAILABLE FOR BRANCHING                                      +17.50 + (-23.83) + (+8.75) + (-23.83) + (+8.75) + (+95.27)         ΔH° = +82.61 Kcal                                                NOTE:                                                                         PRODUCT YIELD ○ = (4) MOLES H.sub.2 +(3) MOLES H.sub. 2 O.sub.2        4H.sub.2 + 2O.sub.2 = (4 × 68.3 Kcal) =                                                          273.20 Kcal                                          3H.sub.2 O.sub.2 = (3 × 32.58 Kcal) =                                                             97.74 Kcal                                                                   370.94 Kcal                                          DETAIL ON REACTIONS                                                            ##STR27##                                                                           ΔH°.sub.f : 2(-68.30)                                                             O -59.55 -59.55                                               S°.sub.f : 2(+16.71)                                                                   2 (+31.21) + 38.47 +38.47                                    ΔH°.sub.RE : -119.10 - (-136.6) = +17.50 Kcal/Mole -             EQN                                                                           ΔS°.sub.RE : +139.36 - (+33.42) = +105.94 CAL-MOLE               × DEG                                                                   TΔS° : 298.0.sub.DEG × 105.94/1000 = +31.57                Kcal/Mole - EQN                                                               ΔG° = ΔH° -TΔS° =+17.50 -              (+31.57) = -14.07 Kcal/Mole - EQN                                       ##STR28##                                                                                ΔH°.sub.f : -68.3 O -59.55                                                        -32.58 -59.55 -59.55                                          S°.sub.f : +16.71 +49.0 +38.47                                                         +55.60 +38.47 +38.47                                    ΔH°.sub.RE : -151.68 - (-127.85) = -23.83 Kcal/Mole -            EQN                                                                           ΔS°.sub.RE : +132.54 - (+104.18) = +28.00 CAL-MOLE -             EQN                                                                           TΔS° 298.0.sub.DEG × 28.0/1000 = +8.45                     Kcal/Mole - EQN                                                               ΔG° = ΔH° -TΔS° = -23.83 -             (+8.45) = -32.28 Kcal/Mole - EQN                                        ##STR29##                                                                                ΔH°.sub.f : -68.3 -59.55                                                          O -59.55 -59.55                                               S°.sub.f : +16.71 +38.47                                                               +31.21 +38.47 +38.47                                    ΔH°.sub.RE : -119.1 - (-127.85) = +8.75 Kcal/Mole -              EQN                                                                           ΔS°.sub.RE : +108.15 - (+55.18) = +52.97 CAL - MOLE              × DEG.                                                                  TΔS° 298.0.sub.DEG × 52.97/1000 = +15.78                   Kcal/Mole - EQN                                                               ΔG° + ΔH° - TΔS° = +8.75 -             )+15.78) = -7.03 Kcal/Mole - EQN                                        ##STR30##                                                                                ΔH°.sub.f : -68.3 -59.55 -59.55                                                   -32.58 -59.55                                                 S°.sub.f : +16.71 +38.47 +38.47                                                        + 55.60 +38.47                                          ΔH°.sub.RE : -92.13 - (-187.40) = +95.27 Kcal/Mole -             EQN                                                                           ΔS°.sub.RE : +94.07 - (+93.65) = +0.42 CAL - MOLE                × DEG                                                                   TΔS° 298.0.sub.DEG × 0.42/1000 = 0.13 Kcal/Mole            - EQN                                                                         ΔG° = ΔH° - TΔS° = +95.27              -0.13 = +95.14 Kcal/Mole EQN                                                  ○H°-+17.50 + (-23.83) + (8.75) + (-23.83) + (+8.75)             + (95.27)                                                                        ΔH° = +82.61 Kcal                                      NOTE:                                                                                (A.) PRODUCT YIELD = (4) MOLES H.sub.2 + (3) MOLES H.sub.2                    O.sub.2                                                                4 H.sub.2 +2O.sub.2 = (4 × 68.3 Kcal) =                                                         273.20 Kcal                                           3 H.sub.2 O.sub.2 = (3 × 32.58 Kcal) =                                                           97.74 Kcal                                           TOTAL =                 370.94 Kcal                                                  (B.) THEREFORE: 370.94 - 82.61 - 136.60                                        = 219.21 (Kcal -  Net)                                                        ##STR31##                                                             __________________________________________________________________________

CHAIN REACTION EXAMPLE NO. 5

When water vapor alone, or when air including oxygen, and water vapor,are supplied to one of the reaction chambers, chain reactions occurwhich involve only the water vapor. The following example will considersuch a chain reaction. In actual practice the reactions may follow alarge number of branching patters, but it has been determined that theexample set forth below includes the principal reaction mechanisms whichoccur.

Initially, the activation energies of the bonds of interest will betabulated:

    ______________________________________                                        BONDS OF INTEREST                                                                          Activation Energies                                                           For Activated Complexes                                                       in Kcal                                                          ______________________________________                                        1. H--O.sub.2 = 47.0                                                                         2.82                                                           2. HO--O 64.0  3.84                                                           3. HO--OH = 51.0                                                                             3.06                                                           4. HO.sub.2 --H = 90.0                                                                       5.40                                                           5. H--H = 104.2                                                                              6.25                                                           6. O--O = 119.1                                                                              7.15                                                           7. H--OH = 119.0                                                                             7.14                                                           8. H--O = 102.0                                                                              6.12                                                           ______________________________________                                    

The activation energy will amount of ˜5.5 percent minimum of the bondenergy of the bond to be broken. Then, for the reaction A+BC⃡AB+C, if thereaction is exothermic from left to right, the activation energyestimated by the semiempirical method will be ˜5.5 percent of themolecule BC. The activation energy of the reverse endothermic step willbe this amount, plus the heat of the reaction. For our purposes, we usedthe figure of 0.06 (6.0) percent for our calculations. ##STR32##

INPUT ELECTRICAL ENERGY

(1) We have determined that we would like to supply the equivalent of315.0 Kcal per second, so we convert this:

    ______________________________________                                        (a) 1.0 Kcal - Sec = 4.186 Kwatts - sec.                                       ##STR33##                                                                    ______________________________________                                    

(2) 1318.59 Kwatts-sec≡1.318,590 Joules per sec.

(3) Joule-sec.=1.5258×10³³ quanta.

(4) ##EQU6## (5) 1,318,590 (Joules-sec.)×2.53455×10⁹ (quanta) ##STR34##(6) "Power" will be obtained in watts if W is expressed in joules (10⁷ergs) and t in seconds. ##EQU7## (7) INFRARED=2.5 (Peak)=˜24.0Kcal/Mole/Photons (8) U.V.=1847A=˜155.0 Kcal/Mole/Photons

    ______________________________________                                        155.0                                                                         24.0                                                                          24.0                                                                          24.0                                                                                    315.0 Kcal/sec (= DISTRIBUTION)                                     24.0                                                                          24.0                                                                          20.0                                                                          20.0                                                                          ______________________________________                                    

A. INPUT

315.0 (Kcal-Per-Unit-Time)

B. OUTPUT (Per-Same-Unit-Time) (Assuming 100% efficiency on reactionsshown.) ##EQU8## C. OUTPUT (Per-Same-Unit-Time) (Assuming 50.0%efficiency on reactions shown.) ##EQU9##

In summary, the apparatus described hereinabove may clearly be designedto provide the staged and compartmentalized irradiation of reactions toobtain conditions which are favorable to the reaction mechanisms ofinterest. Different radiation frequencies may be employed at the inputfeedstock area and at the output feedstock area to enhance the desiredreaction. Certain selected reactions have been considered in somedetail. Other reactions involving breaking molecular bonds andsubstituting new elements or radicals may be implemented by the sametype of technique used in the apparatus as disclosed herein or similarapparatus. Typical products which may be input feedstocks includemethane, ethane, propane, isobutane, N-pentane, isopentane, neopentane,and the alkyl amines. The apparatus as described in the presentapplication are also particularly suited to hydrogenation and olefinformation, the dehydration of alcohols, addition reactions of olefins,and to reactions involving polysubstituted saturated hydrocarbons,benzene, unsaturated hydrocarbons including the alkyne series, alcohols,carboxylic acids, aldehydes, and ketones.

For completeness, certain matters relating to the gas discharge tubesand certain laser-type materials which may be used will now be reviewed.Initially, as mentioned above, the gas discharge tubes are preferablymade of quartz and are mercury gas discharge lamps. One typical lampavailable from Westinghouse is rated by the manufacturer at 39.0 watts,0.420 amperes, for 115 volts A.C. operation. The emitted ultravioletradiations are rated by the manufacturer at 38.5 percent of input power,or at about 15+watts. Quartz, depending on its quality will transmitultraviolet radiations with a cut-off of between 1000 Angstrom units and2,000 Angstrom units.

The lines in the ultraviolet emission spectrum of mercury are set forthbelow, with particularly strong lines appearing at 2536 A° and at 1849A°.

    ______________________________________                                        LINES IN THE ULTRAVIOLET                                                      EMISSION SPECTRUM OF MERCURY                                                  (Wavelength in Angstrom Units)                                                ______________________________________                                        1269.7      2399.4         3125.6                                             1527.0      2482.7         3131.6                                             1592.0      2534.8         3131.8                                             1599.0      2536.0         3341.5                                             1650.0      2652.0         3650.2                                             1677.9      2698.9         3654.8                                             1783.3      2752.8         3662.8                                             1798.7      2803.5         3663.3                                             1849,0      2847.7         3906.4                                             1942.0      2893.6         3983.9                                             2224.7      2967.3         4046.6                                             2378.3      3021.5                                                            ______________________________________                                    

Four known laser type materials which may be used are as follows:

1. Aluminum Oxide (Al₂ O₃) doped with chromium (Cr³⁺), requiring inputpumping radiation of from 0.32 to 0.42 microns, or from 3200 A° to 4200A°, and having a fundamental output wavelength of 6934 A°.

2. Yttrium Oxide (Y₂ O₃) doped with europium (Eu³⁺), requiring inputpumping radiation of from 2000 A° to 2800 A°, and having an outputwavelength of 6113 A°.

3. Calcium Tungstate (CaWO₄) doped with erbium (Er³⁺) requiring inputpumping radiation between 2000 A° and 2800 A° and having a fundamentaloutput wavelength of 16,120 A°.

4. Aluminum Oxide (Al₅ O₁₂) doped with erbium (Er³⁺) requiring inputpumping radiation of between 3200 A° and 4200 A°, and having afundamental output wavelength of 16,602 A°.

Considering Example No. 1 and Example No. 2, it is clear that mercuryvapor spectral lines from 1942 A° through 2803.5 A° are available tosupply pumping radiation for Example No. 2; and that mercury lines3125.6 through 4046.6 are available for pumping Example No. 1.

Concerning another point, the use of the spheres of laser type materialmounted on the quartz envelope of the mercury vapor tube has been noted.As discussed in detail, the mercury vapor discharge provides the radiantenergy to pump the laser type material to the desired excited state toinitiate coherent radiation. Instead of the mercury vapor discharge, thepumping energy for the laser-type material spheres may be provided fromheated filaments coated with mullite suitably doped to provide thedesired pumping frequency. The filaments could be of the configurationdisclosed in FIG. 16, coated with an outer transparent sealing coating,to which the spheres could be secured as shown in FIG. 30, for example.Suitable variation in operating conditions could then be obtained byvarying the power applied to the filaments, and their resultanttemperature, and output radiation.

In closing, it is to be understood that the principles set forth in theforegoing description may be implemented by a number of differentapparatus, with the constructions and materials specified herein onlybeing exemplary of the types of apparatus and materials which may beemployed. Reaction chambers of different configurations, and differentlaser type materials, as well as different feedstocks and products couldbe employed.

I claim:
 1. A radiation apparatus comprising:a filament composed atleast in part of means including solid state material for producingsubstantially coherent output radiation at a predetermined frequency;said filament including semi-reflective surface means extendinggenerally concentric with the axis of said filament, saidsemi-reflective surface means including generally perpendicular surfacesspaced apart by a distance substantially equal to an integral number ofhalf-wave lengths at said predetermined frequency.
 2. An apparatus asdefined in claim 1 wherein two concentric semi-reflective surfaces areprovided.
 3. An apparatus as defined in claim 1 wherein said filament ismade up of a central resistive wire and an outer coating of said solidstate material for producing substantially coherent radiation.
 4. Anapparatus as defined in claim 1 further comprising:means for applyingpumping energy to said solid state material to raise said material to anexcited state for producing coherent radiation.
 5. An apparatus asdefined in claim 1 further comprising:a reaction chamber, means formounting a plurality of said filaments in said reaction chamber; andmeans for applying pumping energy to said solid state material to raisesaid material to an excited state, whereby said reaction chamber isflooded with output radiation from said solid state material.
 6. Anapparatus as defined in claim 5 wherein said means for producingsubstantially coherent radiation includes solid state materials havingdifferent radiating frequencies in different ones of said filaments,whereby radiation of at least two different frequencies is applied tosaid reaction chamber.
 7. An apparatus as defined in claim 6 furthercomprising means for supplying feedstock to said reaction chamber,thereby producing media discontinuities within said chamber, whereby sumand difference frequencies derived from different radiation frequenciespresent in said reaction chamber, are formed and are coupled to saidfeedstock.
 8. An apparatus as defined in claim 7 further comprisingmeans for supplying to said reaction chamber feedstock having anabsorption band at the sum frequency of two or more radiations presentin said reaction chamber, to cause dissociation of said feedstock.
 9. Anapparatus as defined in claim 5 further comprising means for supplyingfeedstock having an absorption band at said predetermined frequency ofsaid radiation, to said reaction chamber, to cause dissociation of saidfeedstock.
 10. An apparatus as defined in claim 9 further comprisingmeans for supplying a second feedstock to said reaction chamber to reactwith one or more of the dissociation products of the first feedstock.11. An apparatus as defined in claim 1 further comprising a plurality ofgas discharge tubes, and wherein a plurality of said filaments arehelically wrapped around said gas discharge tubes.
 12. An apparatus asdefined in claim 11 wherein said gas discharge tubes are mercury vaporgas discharge tubes.
 13. An apparatus as defined in claim 1 wherein saidsolid state material includes host and sensitizer material for receivingincoherent radiant energy and for radiating substantially coherentmonochromatic radiation at a different frequency than that of the inputradiant energy.
 14. An apparatus as defined in claim 1 wherein means areprovided for directing radiation outward from said filamentsubstantially transverse to the axis thereof.
 15. An apparatus forcontrolled photochemical reactions comprising:a reaction chamber; meansfor supplying feedstock to said reaction chamber, said feedstock havinga predetermined frequency absorption band or bands; and means forflooding said reaction chamber with radiation within at least one of theabsorption bands of said feedstock; said means including at least onegas discharge tube having output radiation of a lower frequency thansaid predetermined band or bands and means in physical proximity to saidgas discharge tube and also exposed to said reaction chamber forreceiving said lower frequency radiation from said gas discharge tubeand for supplying intense radiation to said reaction chamber within saidpredetermined band or bands.
 16. An apparatus for controlledphotochemical reactions comprising:a reaction chamber; means forsupplying feedstock to said reaction chamber, said feedstock havingpredetermined absorption bands; means including a plurality of gasdischarge tubes for flooding said reaction chamber with radiation withinat least one of the absorption bands of said feedstock; and meansincluding solid state material in close proximity to said gas dischargetubes for receiving pumping energy from said gas discharge tubes and forradiating substantially coherent energy into said reaction chamber at adifferent frequency.
 17. An apparatus as defined in claim 16 whereinsaid solid state material is in the form of filaments wound onto saidgas discharge tubes.
 18. An apparatus as defined in claim 16 whereinsaid solid state material is in the form of spheres mounted on said gasdischarge tubes.
 19. An apparatus as defined in claim 16 wherein saidsolid state material intercepts only a fraction of the radiation fromsaid gas discharge tubes, whereby said reaction chamber is flooded withradiation of different frequencies forming sum and differencefrequencies at the media discontinuities formed by the presence of thefeedstock; and wherein said gas discharge tubes and said solid statematerial include means for producing at least one of the sum frequenciesin an absorption band of said feedstock.
 20. An apparatus as defined inclaim 16 further comprising reflective coating means associated withsaid solid state material for increasing the coherency of saidradiation.
 21. An apparatus as defined in claim 20 wherein saidreflective coating means reflects from 70% to 90% of incident visibleradiation.
 22. An apparatus as defined in claim 16 further comprisingreflective coating means associated with said solid state material forreflecting infared and visible frequencies and for transmitting shorterwavelength ultraviolet radiations to supply coherent harmonic radiationsto said reaction chamber.
 23. An apparatus for efficiently accomplishingphotochemical reactions comprising:a reaction chamber; means forapplying feedstock to said reaction chamber, said feedstock havingpredetermined frequency absorption band or bands; means located withinsaid chamber for flooding said reaction chamber with substantiallycoherent energy within one of the absorption bands of said feedstock atenergy levels sufficient to dissociate said feedstock, said radiationsupplying means including solid state material; and low cost incoherentenergy source means immediately adjacent said supplying means forpumping said solid state material to an excited state.
 24. A source ofradiant energy comprising:means including a sphere of solid statematerial for producing substantially coherent radiations; asemi-reflective coating on at least the major portion of the outersurface of said sphere; and means for pumping said solid state materialto an excited state, whereby substantially coherent energy is radiatedthrough said semi-reflective coating from said solid state material toan excited state, whereby substantially coherent energy is radiatedthrough said semi-reflective coating from said material.
 25. A source ofradiant energy as defined in claim 24 wherein a plurality of said coatedspheres are provided, and wherein said pumping means directs pumpingradiation into said material through a portion of the surface of each ofsaid spheres that is not coated with said semi-reflecting coating.
 26. Asource of radiant energy as defined in claim 25 wherein transparentenvelope means are provided for supporting said spheres, and saidpumping means supplies radiant energy to said spheres through saidtransparent envelope.
 27. A source of radiant energy as defined in claim26 wherein said pumping means is a mercury vapor gas discharge tube. 28.A source of radiant energy as defined in claim 26 wherein said pumpingmeans includes means for converting electrical power to radiant energyof the proper high frequency required to pump said laser material to theexcited state.
 29. A source of radiant energy as defined in claim 24wherein said semi-reflective coating reflects from 70% to 90% of theincident visible radiation.
 30. A source of radiant energy as defined inclaim 24 wherein said semi-reflective coating comprises means forreflecting infrared and visible frequencies and for transmitting shorterwavelength ultra-violet radiations whereby coherent harmonic radiationsemanate from said spheres.
 31. An apparatus for controlled photochemicalreactions including the radiant energy source as defined in claim 24 andfurther comprising:means defining a reaction chamber for receiving themajor portion of the radiation from said source; means for supplying areactant to said chamber, said reactant having a frequency absorptionband corresponding to the frequency of radiation from said source. 32.An apparatus for obtaining hydrogen or hydrogen peroxide from watervapor comprising:means for directing water vapor through a predeterminedreaction zone, said water vapor having predetermined absorptionfrequency bands; means including at least one gas discharge tube withinsaid reaction zone, for flooding said reaction zone with radiationwithin at least one of said absorption frequency bands, at sufficientlyhigh intensities to produce combustible hydrogen or hydrogen peroxidefrom said water vapor, said means for flooding said reaction zone withradiation further including means in immediate proximity with said gasdischarge tube for receiving radiation from said gas discharge tubehaving a predetermined frequency output, and for supplying higherfrequency radiation to said reaction zone.
 33. An apparatus as definedin claim 32 further comprising solid state means for producingsubstantially coherent output radiation within at least one of saidabsorption bands.
 34. An apparatus as defined in claim 32 wherein saidgas discharge means includes mercury vapor gas discharge means.
 35. Anapparatus as defined in claim 32 further comprising means for directingsaid water vapor into intimate reactive proximity to said means forsupplying higher frequency radiation into said reaction zone.
 36. Anapparatus as defined in claim 32 further comprising means forcontinuously flowing water vapor through said reaction zone tocontinuously form combustible hydrogen or hydrogen peroxide.
 37. Anapparatus as defined in claim 32 wherein said gas discharge means iselongated; and wherein said means for receiving radiation from said gasdischarge means is also elongated, and is spaced around said gasdischarge means, and includes means for radiating said higher frequencyradiation outward substantially transverse to the elongated gasdischarge means.
 38. An apparatus for controlled photochemical reactionscomprising:a reaction chamber; means for supplying feedstock to saidreaction chamber, said feedstock having a predetermined energyabsorption vs. frequency characteristic, including at least one highenergy absorption region; means located within said radiation chamberfor flooding said reaction chamber with high intensity radiation withinsaid high energy absorption region of said feedstock; said radiationflooding means including solid state means having outer surfaces ofsubstantially circular cross-section for producing substantiallycoherent output radiation within or in immediate proximity to saidreaction chamber; and means for exciting said means for producingsubstantially coherent radiation to an excited state to radiaterelatively coherent high frequency radiation through said outer surfacesat intensity levels sufficient to modify the form of a substantialproportion of said feedstock.
 39. An apparatus as defined in claim 38wherein said means for producing substantially coherent radiation is inthe form of a plurality of elements of solid state material spaced apartwithin said reaction chamber.
 40. An apparatus as defined in claim 38wherein said solid state means are substantially spherical.
 41. Anapparatus as defined in claim 38 wherein said solid state means areelongated and are of substantially constant circular cross section. 42.An apparatus as defined in claim 41 wherein said solid state meansinclude cylindrical rods.
 43. An apparatus as defined in claim 41wherein said solid state means include cylindrical filaments.
 44. Anapparatus as defined in claim 41 wherein said solid state means have asubstantially cylindrical outer radiating surface.
 45. An apparatus asdefined in claim 38 wherein semireflective coating means are provided onthe outside of said solid state means.
 46. An apparatus as defined inclaim 38 wherein semireflective coating means are provided on said solidstate means to enchance the production of high frequency harmonicradiation and to supply it to said reaction chamber, saidsemi-reflecting coating being formed of material which is reflective tofrequencies below ultraviolet radiation and which is relativelytransparent to ultraviolet radiation.
 47. An apparatus for controlledphotochemical reactions comprising:a reaction zone; means for supplyingfeedstock to said reaction zone, said feedstock having a predeterminedenergy absoprtion vs. frequench characteristic, including at least onehigh energy absorption region; means located inside said reaction zonefor flooding said reaction zone with high intensity radiation withinsaid high energy absorption region of said feedstock; said meansincluding at least one elongated gas discharge device within saidreaction zone; and means spaced around said gas discharge device forreceiving radiation from said gas discharge device and for radiatinghigh intensity radiation having a higher frequency content than theradiation from said gas discharge device, into said reaction zone. 48.An apparatus as defined in claim 47 including means for supplying watervapor to said reaction zone and means for drawing off hydrogen orhydrogen peroxide from said reaction zone.
 49. In a system forsubjecting material to high frequency radiation;reaction chamber meansfor holding a reactant having a predetermined high frequency absorptionband; a high power source of lower frequency radiation; interface meanslocated between said source of lower frequency radiation and saidreaction chamber means for receiving said lower frequency radiation andfor flooding said reaction chamber with high intensity radiation in saidpredetermined absorption band, at an intensity level sufficient todissociate said reactant, said interface means including means mountedadjacent said reaction chamber for reflecting the major portion of saidlower frequency radiation but transmitting the major portion ofradiation at said predetermined high frequency.
 50. A system as definedin claim 49 wherein said reflecting means is a thin metal layer.
 51. Asystem as defined in claim 49 wherein said system includes means forsupplying water vapor as said reactant to said reaction chamber, andmeans for drawing off hydrogen and/or hydrogen peroxide from saidreaction chamber.
 52. An apparatus for controlled photochemicalreactions comprising:a reaction zone; means for supplying water vapor tosaid reaction zone, said water vapor having predetermined absorptionband or bands in the ultra-violet frequency spectrum; at least oneelongated gas discharge tube mounted within said reaction zone andproducing a predetermined lower frequency radiation output; and meansspaced around said gas discharge tube for receiving said lower frequencyradiation output from said gas discharge tube, and for flooding saidreaction zone with higher frequency output radiation within saidpredetermined absorption band or bands in the ultraviolet frequencyspectrum, and at an intensity level sufficient to dissociate the greaterportion of said water vapor and to form hydrogen and/or hydrogenperoxide.